CN115666938A - Layer element suitable as an integrated back sheet element of a photovoltaic module - Google Patents
Layer element suitable as an integrated back sheet element of a photovoltaic module Download PDFInfo
- Publication number
- CN115666938A CN115666938A CN202180037440.2A CN202180037440A CN115666938A CN 115666938 A CN115666938 A CN 115666938A CN 202180037440 A CN202180037440 A CN 202180037440A CN 115666938 A CN115666938 A CN 115666938A
- Authority
- CN
- China
- Prior art keywords
- layer
- copolymer
- ethylene
- layer element
- ethylene copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- -1 polyethylene Polymers 0.000 claims description 186
- 229920001038 ethylene copolymer Polymers 0.000 claims description 177
- 239000000203 mixture Substances 0.000 claims description 169
- 229920001577 copolymer Polymers 0.000 claims description 134
- 229920001155 polypropylene Polymers 0.000 claims description 122
- 239000004698 Polyethylene Substances 0.000 claims description 98
- 229920000573 polyethylene Polymers 0.000 claims description 97
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 93
- 239000005977 Ethylene Substances 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 79
- 239000004743 Polypropylene Substances 0.000 claims description 69
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 67
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 61
- 238000001125 extrusion Methods 0.000 claims description 47
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 46
- 238000003475 lamination Methods 0.000 claims description 41
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 22
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 22
- 239000004711 α-olefin Substances 0.000 claims description 22
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 20
- 230000001681 protective effect Effects 0.000 claims description 19
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 18
- 238000005538 encapsulation Methods 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Chemical class 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 4
- 229940018557 citraconic acid Drugs 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 101710149624 Pectinesterase B Proteins 0.000 claims 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims 2
- 125000000962 organic group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 435
- 229920000642 polymer Polymers 0.000 description 68
- 239000000654 additive Substances 0.000 description 51
- 230000008569 process Effects 0.000 description 45
- 239000000049 pigment Substances 0.000 description 43
- 239000010408 film Substances 0.000 description 42
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 40
- 238000012360 testing method Methods 0.000 description 34
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 29
- 239000000945 filler Substances 0.000 description 29
- 239000003063 flame retardant Substances 0.000 description 28
- 229920000034 Plastomer Polymers 0.000 description 20
- 239000006229 carbon black Substances 0.000 description 20
- 235000019241 carbon black Nutrition 0.000 description 20
- 239000000178 monomer Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 14
- 239000012790 adhesive layer Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 12
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 12
- 239000008393 encapsulating agent Substances 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 230000006870 function Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229920001384 propylene homopolymer Polymers 0.000 description 7
- LSZMEVZPFPOJIT-UHFFFAOYSA-N 2,2-dimethoxyethoxy(ethenyl)silane Chemical compound COC(CO[SiH2]C=C)OC LSZMEVZPFPOJIT-UHFFFAOYSA-N 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 239000012963 UV stabilizer Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 238000003490 calendering Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000011179 visual inspection Methods 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000010467 ester pyrolysis Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- FXSUTKNIHXGZFF-UHFFFAOYSA-N 1-ethenyl-2-methylcyclohexane Chemical compound CC1CCCCC1C=C FXSUTKNIHXGZFF-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920006771 PE-C Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004596 additive masterbatch Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/08—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2331/00—Polyvinylesters
- B32B2331/04—Polymers of vinyl acetate, e.g. PVA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
- B32B37/1018—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using only vacuum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention relates to a layer element comprising three layers A, B and C in an A-B-C configuration, wherein layer A and layer B, and layer B and layer C are in adhesive contact with one another. An article, preferably a photovoltaic module, comprising the layer element. A method for producing the layer element, and a method for producing a photovoltaic module comprising the layer element, and the use of the layer element as an integrated backsheet element for a photovoltaic module.
Description
Technical Field
The invention relates to a layer element comprising at least three layers A, B and C constructed in an A-B-C configuration. An article, preferably a photovoltaic module, comprising the layer element as an integrated backsheet element. A method for producing the layer element, and a method for producing the photovoltaic module and the use of the layer element as an integrated backsheet element for a photovoltaic module.
Background
In certain end-use applications, such as outdoor end-use applications, the temperature may vary over a wide range and the article may be exposed to sunlight, thus having special requirements for the polymer article, such as mechanical properties, long-term thermal stability (especially high temperature, barrier properties and uv stability).
For example, photovoltaic (PV) modules, also referred to as solar cell modules, are well known for generating electricity using light and for various applications (i.e., outdoor applications). The type of photovoltaic module may vary. The modules usually have a multilayer structure, i.e. a plurality of different layer elements with different functions. The layer elements of the photovoltaic module can vary in layer material and layer structure. The final photovoltaic module may be rigid or flexible. The layer elements of the above examples may be single layer or multilayer elements. Typically, the layer elements of a PV module are assembled in the order of their functions and then laminated together to form an integrated PV module. Furthermore, there may be adhesive layers between layers of elements or between elements of different layers. A Photovoltaic (PV) module may for example comprise, in the given order, a protective front layer element (which may be flexible or rigid, e.g. a glass layer element), a front encapsulation layer element, a photovoltaic element, a rear encapsulation layer element, a protective back layer element (also referred to as backsheet element and may be rigid or flexible); and optionally, an aluminum frame, for example. Accordingly, some or all of the layer elements of the PV module (e.g., the front and back encapsulant layer elements, and typically the backsheet layer) are typically made of polymeric materials, such as Ethylene Vinyl Acetate (EVA) based materials, polyester based materials or polyamide based materials, and fluoropolymer based materials.
In the case of articles having multiple layers of elements (e.g., PV modules), the compatibility of the different layer materials can cause problems that reduce the performance of the final article. The properties of the selected layer material may also be insufficient to meet the overall properties desired for the layer element in the end use of the final article. Particularly problematic is the compatibility of the rear encapsulation layer elements and the polymer backsheet element, which can lead to adhesion problems between these layer elements. These adhesion problems are typically addressed by including an additional adhesive layer between the back-encapsulant layer element and the polymeric backsheet layer element. However, the additional layer treatment increases the complexity of the lamination process, which leads to increased energy costs and time consumption. Accordingly, the art has sought to reduce the total number of layers in the PV module lamination process to reduce production costs and energy consumption.
WO2018/141672 discloses an article, suitably a PV module, having a layer element comprising a polyethylene-based layer and a polypropylene-based layer in adhesive contact with each other, which can be used as an integrated backsheet for a PV module. Thus, the polyethylene-based layer may be used as a back-encapsulation layer element and the polypropylene-based layer may be used as a polymer backsheet element. The layer element of WO2018/141672 shows acceptable adhesion between the polyethylene-based layer and the polypropylene-based layer.
There is still room for improvement in the balance of improved adhesion between the encapsulant layer element and the polymer backsheet element, as well as in reducing the number of layers in the PV module to reduce the complexity of the lamination process and reduce production costs and energy consumption.
In the present invention, it has surprisingly been found that a layer element comprising three layers a-B-C, wherein an adhesive layer B comprising an ethylene- α -olefin copolymer-based composition is sandwiched between a polyethylene-based layer a and a polypropylene-based layer C, can exhibit improved adhesion compared to a two-layer structure in which only one additional layer is present in the layer element, and can ensure easy handling and lamination thereof while reducing production costs and energy consumption.
Disclosure of Invention
The invention relates to a layer element comprising layers A, B and C constructed in an A-B-C configuration, wherein,
-layer a comprises a polyethylene composition (PE-a) comprising an ethylene copolymer selected from the group consisting of:
-an ethylene copolymer (PE-a) having silane group containing units, said ethylene copolymer (PE-a) having silane group containing units; or
-copolymers of ethylene with polar comonomer units (PE-A-b), said polar comonomer units being selected from (C) 1 -C 6 ) Alkyl acrylate or (C) 1 -C 6 ) Alkyl (C) 1 -C 6 ) -one or more of alkyl acrylate comonomer units, said copolymer of ethylene with polar comonomer units (PE-A-b) additionally having silane group(s) containing units,
thus, the ethylene copolymer (PE-A-a) is different from the ethylene copolymer (PE-A-b);
-layer B comprises a polyethylene composition (PE-B) comprising an ethylene copolymer selected from the group consisting of:
a density of 850kg/m 3 To 905kg/m 3 And comonomer units selected from one or more alpha-olefins having from 3 to 12 carbon atoms (PE-B-a); or
-density of 850kg/m 3 To 905kg/m 3 A copolymer of ethylene and comonomer units (PE-B) selected from one or more alpha-olefins having from 3 to 12 carbon atoms, said copolymer of ethylene and comonomer units (PE-B) additionally having silane group(s) containing units; or alternatively
A density of 850kg/m 3 To 905kg/m 3 Ethylene and comonomer ofA copolymer of units (PE-B-c) selected from one or more alpha-olefins having from 3 to 12 carbon atoms, said copolymer of ethylene and comonomer units (PE-B-c) additionally having functional group-containing units derived from at least one unsaturated carboxylic acid and/or anhydride, metal salt, ester, amide or imide thereof and mixtures thereof; and
-layer C comprises a polypropylene composition (PP-C) comprising a propylene polymer (PP-C-a),
wherein layers a and B, and layers B and C are in adhesive contact with each other.
Furthermore, the present invention relates to an article comprising a layer element as described above or below. The article is preferably a photovoltaic module.
Still further, the present invention relates to a method for producing a layer element as described above or below, comprising the steps of:
-bonding together the layers a, B and C of the layer element in a configuration a-B-C by extrusion or lamination; and
-recovering the formed layer element.
Furthermore, the present invention relates to a process for producing an article as a Photovoltaic (PV) module as described above or below, comprising the steps of:
-assembling the photovoltaic element, the layer element and optionally further layer elements into a Photovoltaic (PV) module assembly;
-laminating the layer elements of the Photovoltaic (PV) module assembly at high temperature to bond the elements together; and
-recovering the Photovoltaic (PV) module obtained.
Finally, the invention relates to the use of a layer element as described above or below as an integrated backsheet element for a photovoltaic module comprising a photovoltaic element and said layer element, wherein the photovoltaic element is in adhesive contact with layer a of the layer element.
Drawings
Fig. 1 is a schematic diagram of a typical PV module of the invention, comprising a protective front layer element (1), a front encapsulant layer element (2), a photovoltaic element (3) and a layer element of the invention ((4) + (5) + (6) in combination) showing layers a, B and C, where layer a serves as the rear encapsulant layer element (4), layer C serves as the protective rear layer element (6) and layer B serves as the adhesive layer (5).
Detailed Description
Definition of
An olefin homopolymer is a polymer consisting essentially of one olefin monomer unit. Due to impurities, especially in commercial polymerization processes, the olefin homopolymer may comprise up to 0.1mol% of comonomer units, preferably up to 0.05mol% of comonomer units, most preferably up to 0.01mol% of comonomer units.
In this sense, a propylene homopolymer is a polymer consisting essentially of propylene monomer units, whereas an ethylene homopolymer is a polymer consisting essentially of ethylene monomer units.
Olefin copolymers are polymers that contain small molar amounts of more than one comonomer unit in addition to olefin monomer units.
Thus, copolymers of propylene contain a molar majority (molar majority) of propylene monomer units, while copolymers of ethylene contain a molar majority of ethylene monomer units.
An olefin random copolymer is a copolymer having a molar majority of the olefin monomer units, wherein the comonomer units are randomly distributed in the polymer chain.
Heterophasic polypropylenes are propylene-based copolymers having a crystalline matrix phase, which may be a propylene homopolymer or a random copolymer of propylene and at least one alpha-olefin comonomer, and an elastomeric phase dispersed therein. The elastomeric phase may be a propylene copolymer having a significant amount of comonomer which is not randomly distributed in the polymer chain but is distributed in a comonomer rich block structure and a propylene rich block structure.
Heterophasic polypropylene is generally different from monophasic propylene copolymer in that it shows two different glass transition temperatures Tg, which are attributed to the matrix phase and the elastomeric phase.
Plastomers are polymers that combine the properties of elastomers and plastics, such as rubber-like properties and processability of plastics.
The ethylene plastomer is a plastomer having a majority by mole of ethylene monomer units.
A layer element in the sense of the present invention is a structure with more than one layer and has a defined function which serves a specific purpose in an article comprising said layer element. In the field of PV modules, a layer element is a structure of more than one layer that provides one of a variety of functions, such as external protection (i.e., protective front layer element or protective back layer element), encapsulation of photovoltaic elements (i.e., front encapsulation layer element or rear encapsulation layer element), and energy conversion (i.e., photovoltaic element). The layer elements may include other components than layers, such as brackets, spacers, frames, and the like.
The integrated backsheet element of a PV module is a structure of more than one layer, which contains more than one function of the PV module. Preferably, the integrated backsheet element comprises the outer protective function of the protective backsheet element and the photovoltaic element encapsulation function of the back encapsulation layer element. These functions are typically included in different layers of the integrated backplane element.
By two layers in adhesive contact is meant that the surface of one layer is in direct contact with the surface of the other layer without any layers or any spacers between the layers.
"different" in the context of the present invention means that the two polymers differ in at least one property or structural element.
Layer element
The layer element of the present invention comprises three layers a, B and C configured as a-B-C. This means that layer a is in adhesive contact with layer B on one surface of layer B and layer B is in adhesive contact with layer C on the other surface of layer B. Thus, layer a and layer C are not in adhesive contact with each other. But layer B is sandwiched between layer a and layer C.
In one embodiment, the layer element consists of a layer A, a layer B and a layer C configured as A-B-C. In the described embodiment, the layer element is a three-layer element.
In another embodiment, the layer element may comprise more than one layer in addition to layer a, layer B and layer C. These additional layers may be added to the surface of layer a that is not in adhesive contact with layer B (i.e., layer X), or to the surface of layer C that is not in adhesive contact with layer B (i.e., layer Y), or to both (i.e., layer X and layer Y).
Possible configurations are X-A-B-C, A-B-C-Y and X-A-B-C-Y.
The layer X may be more than one additional layer X, for example 1, 2, 3 or 4 additional layers X, preferably one additional layer X. Layer X may be the same as layer a or different from layer a.
The layer Y may be more than one additional layer Y, for example 1, 2, 3 or 4 additional layers Y, preferably one additional layer Y. Layer Y may be the same as layer C or different from layer C.
Typically, layers a and C are the same thickness or greater than layer B.
In the three-layer element, the thickness of layer a is preferably 30% to 50% of the total thickness of the three-layer element.
In the three-layer element, the thickness of layer B is preferably 5% to 33.3% of the total thickness of the three-layer element.
In the three-layer element, the thickness of layer C is preferably 30% to 50% of the total thickness of the three-layer element.
The thickness ratio of layers a: B: C in the three-layer element is preferably 45 to 33.3.
In a five layer element, each layer X, a, B, C, Y is preferably independently 10-30% of the total thickness of the three layer element.
The thickness ratio of layer X: a: B: C: Y in the five-layer element is preferably 20.
The total thickness of the layer elements is generally 325 μm to 2000 μm, preferably 450 μm to 1750 μm, most preferably 600 μm to 1500 μm.
At least one layer of the layer element may comprise one or more of a filler, pigment, carbon black or flame retardant as defined below, preferably at least one layer of the layer element comprises one or more of a filler, pigment, carbon black or flame retardant, more preferably at least one or both of layer a and layer C, preferably at least layer C comprises a pigment or filler, preferably a pigment, as defined below.
Layer A
Layer a comprises, preferably consists of, a polyethylene composition (PE-a).
The polyethylene composition (PE-a) comprises an ethylene copolymer selected from the group consisting of:
-an ethylene copolymer (PE-a) having silane group containing units; or alternatively
Copolymers of ethylene with one or more polar comonomer units (PE-A-b), the polar comonomer units being chosen from (C) 1 -C 6 ) Alkyl acrylate or (C) 1 -C 6 ) Alkyl (C) 1 -C 6 ) -alkyl acrylate comonomer units, the copolymer of ethylene with polar comonomer units (PE-A-b) additionally having silane group(s) containing units,
thus, the ethylene copolymer (PE-A-a) is different from the ethylene copolymer (PE-A-b).
The alternative ethylene copolymers (PE-A-a) and ethylene copolymers (PE-A-b) both have silane group-containing units.
The silane group containing units may be present as comonomer units of the ethylene copolymer or as a compound chemically grafted to the ethylene copolymer. By "silane group containing comonomer units" is meant herein above, below or in the claims that silane group containing units are present as comonomer units in the ethylene copolymer.
In the case where the silane group-containing unit is incorporated as a comonomer unit into the ethylene copolymer, the silane group-containing unit is copolymerized as a comonomer unit with an ethylene monomer unit during the polymerization of the ethylene copolymer.
In the case where the silane group-containing units are incorporated into the ethylene copolymer by grafting, the silane group-containing units chemically react with the ethylene copolymer (also referred to as grafting) after polymerization of the ethylene copolymer. The chemical reaction (i.e., grafting) is typically carried out using a free radical former such as a peroxide. This chemical reaction may occur before or during the lamination process of the present invention. In general, the copolymerization and grafting of silane group-containing units onto ethylene is a well-known technique and is well documented in the polymer art and within the skill of those in the art.
It is also well known that the use of peroxides in grafting embodiments reduces the Melt Flow Rate (MFR) of the ethylene polymer, since the crosslinking reaction occurs simultaneously. As a result, the grafting embodiment may limit the choice of MFR of the ethylene copolymer as the starting polymer, which may adversely affect the quality of the polymer in the end-use application. Furthermore, the by-products formed from the peroxide during grafting can adversely affect the use of the polyethylene composition (PE-a) in end-use applications.
Copolymerizing the silane group-containing comonomer units into the polymer backbone provides for more uniform incorporation of the units as compared to grafting of the units. Furthermore, in contrast to grafting, copolymerization does not require the addition of peroxide after polymer production.
Thus, silane group-containing units are preferably present in the ethylene copolymer as comonomer units.
That is, in the case of the ethylene copolymer (PE-A-a), the silane group-containing unit is copolymerized as a comonomer unit with the ethylene monomer unit during the polymerization of the ethylene copolymer (PE-A-a).
In the case of the ethylene copolymer (PE-A-b), the silane group-containing units are copolymerized as comonomer units with the polar comonomer units and the ethylene monomer units during the polymerization of the ethylene copolymer (PE-A-b).
The silane group-containing unit (preferably silane group-containing comonomer unit) of the ethylene copolymer (PE-a) or the ethylene copolymer (PE-a-b) is preferably a hydrolyzable unsaturated silane compound represented by the following formula (I):
R 1 SiR 2 q Y 3-q (I)
in the formula:
R 1 is an ethylenically (ethylenically) unsaturated hydrocarbyl, hydrocarbyloxy or (meth) acryloxyhydrocarbyl group,
each R 2 Independently an aliphatic saturated hydrocarbon group,
y, which may be identical or different, is a hydrolyzable organic radical, and
q is 0, 1 or 2;
other suitable silane group containing comonomers are: such as gamma- (meth) acryloxypropyltrimethoxysilane, gamma (meth) acryloxypropyltriethoxysilane, and vinyltriacetoxysilane, or combinations of two or more thereof.
One suitable subgroup of compounds of formula (I) are unsaturated silane compounds, or preferably comonomers of formula (II):
CH 2 ＝CHSi(OA) 3 (II)
wherein each a is independently a hydrocarbyl group having from 1 to 8 carbon atoms, suitably from 1 to 4 carbon atoms.
The silane group(s) containing unit(s) (or preferably comonomer (s)) of the present invention are preferably compounds of formula (II) which are vinyltrimethoxysilane, vinyldimethoxyethoxysilane, vinyltriethoxysilane, more preferably vinyltrimethoxysilane or vinyltriethoxysilane.
The amount of silane group(s) containing units, preferably present as comonomer units, relative to the total amount of monomer units in the ethylene copolymer (PE-a) or ethylene copolymer (PE-a-b) is preferably from 0.01 to 1.5mol%, more preferably from 0.01 to 1.00mol%, still more preferably from 0.05 to 0.80mol%, even more preferably from 0.10 to 0.60mol%, most preferably from 0.10 to 0.50mol%, relative to the total amount of monomer units in the ethylene (PE-a) copolymer or ethylene (PE-a-b) copolymer.
In a preferred embodiment, the ethylene copolymer (PE-a) is an ethylene copolymer having silane group-containing units, preferably having silane group-containing comonomer units. In this embodiment, the ethylene copolymer (PE-a) is free, i.e. free, of polar comonomers as defined for the ethylene copolymer (PE-a-b). Preferably, the silane group containing comonomer units are the only comonomer units present in the ethylene copolymer (PE-A-a). Accordingly, the ethylene copolymer (PE-a) is preferably prepared by copolymerizing ethylene monomer units in the presence of silane group-containing comonomer units using a radical initiator in a high pressure polymerization process.
In said preferred embodiment, the ethylene copolymer (PE-A-a) is preferably a copolymer of ethylene and a silane group containing comonomer unit according to formula (I), more preferably according to formula (II), more preferably selected from vinyltrimethoxysilane, vinyldimethoxyethoxysilane, vinyltriethoxysilane or vinyltrimethoxysilane comonomers. The ethylene copolymer (PE-A-a) is particularly preferably a copolymer of ethylene with a vinyltrimethoxysilane or vinyltriethoxysilane comonomer, most preferably a copolymer of ethylene with vinyltrimethoxysilane.
In another preferred embodiment, the ethylene copolymer (PE-A-b) is a copolymer of ethylene with polar comonomer units selected from (C) 1 -C 6 ) Alkyl acrylates or (C) 1 -C 6 ) Alkyl (C) 1 -C 6 ) -one or more (preferably one) of alkyl acrylate comonomer units and additionally having silane group containing units. Preferably, the silane group containing units are present as comonomer units. Thus, in this embodiment, the ethylene copolymer (PE-A-b) is preferably a copolymer of ethylene with polar comonomer units selected from (C) 1 -C 6 ) Alkyl acrylate or (C) 1 -C 6 ) -alkyl (C) 1 -C 6 ) -one or more (preferably one) alkyl acrylates and additionally having silane group containing comonomer units. Preferably, the polar comonomer units and the silane group containing comonomer units are the only comonomer units present in the ethylene copolymer (PE-a-b). Thus, the ethylene copolymer (PE-a-b) is preferably prepared by copolymerizing ethylene monomer units in a high pressure polymerization process using a free radical initiator in the presence of silane group containing comonomer units.
Preferably, the polar comonomer units of the ethylene copolymer (PE-A-b) are selected from (C) 1 -C 6 ) -alkyl acrylate comonomer units, more preferably selected from Methyl Acrylate (MA), ethyl Acrylate (EA) or Butyl Acrylate (BA) comonomer units, most preferably methyl acrylate comonomer units.
Without being bound by any theory, for example, methyl Acrylate (MA) is the only acrylate that cannot undergo ester pyrolysis reactions because there is no such reaction pathway. Thus, the ethylene copolymer with MA comonomer units (PE-A-b) does not form any harmful free acid (acrylic acid) degradation products at high temperatures, so that the ethylene copolymer comprising methyl acrylate comonomer units (PE-A-b) contributes to good end-article quality and life cycle. This is not the case for vinyl acetate units such as EVA, which can form harmful acetic acid degradation products at high temperatures. In addition, other acrylates such as Ethyl Acrylate (EA) or Butyl Acrylate (BA) may undergo ester pyrolysis reactions, which if degraded, may form volatile olefinic byproducts.
The amount of polar comonomer units present in the ethylene copolymer (PE-a-b) is preferably from 0.5 to 30.0mol%, preferably from 2.5 to 20.0mol%, still more preferably from 5.0 to 15.0mol%, most preferably from 7.5 to 12.5mol%, relative to the total amount of monomer units in the ethylene copolymer (PE-a-b).
The ethylene copolymer (PE-A-b) is preferably a copolymer of ethylene with methyl acrylate, ethyl acrylate or butyl acrylate comonomer units and with vinyltrimethoxysilane, vinyldimethoxyethoxysilane, vinyltriethoxysilane or vinyltrimethoxysilane comonomer units, more preferably with vinyltrimethoxysilane comonomer units or vinyltriethoxysilane comonomer units.
The ethylene copolymer (PE-A-b) is more preferably a copolymer of ethylene with methyl acrylate comonomer units and vinyltrimethoxysilane, vinyldimethoxyethoxysilane, vinyltriethoxysilane or vinyltrimethoxysilane comonomer units, more preferably a copolymer of ethylene with methyl acrylate comonomer units and with vinyltrimethoxysilane or vinyltriethoxysilane comonomer units, and most preferably a copolymer of ethylene with methyl acrylate comonomer units and vinyltrimethoxysilane.
The polyethylene composition (PE-a) enables to reduce the Melt Flow Rate (MFR) of the ethylene copolymer (PE-a) or the ethylene copolymer (PE-a-b), if desired, compared to the prior art, thereby providing a higher flow resistance in the production of the layer a and the layer element of the present invention. As a result, the preferred MFR may further contribute to the quality of the layer element, and of an article comprising the layer element (preferably a PV module), if desired.
Melt flow Rate MFR of the ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-b) 2 Preferably less than 20g/10min, preferably less than 15g/10min, more preferably from 0.1 to 13g/10min, still more preferably from 0.5 to 10g/10min, even more preferably from 1.0 to 8.0g/10min, more preferably from 1.5 to 6.0g/10min.
Shear thinning index SHI of ethylene copolymer (PE-A-a) or ethylene copolymer (PE-A-b) 0.05/300 Preferably from 30.0 to 100.0, more preferably from 40.0 to 80.0, most preferably from 50.0 to 75.0.
The preferred SHI ranges further contribute to the beneficial rheological properties of the polyethylene composition (PE-a).
Thus, the combination of the preferred MFR range and the preferred SHI range of the polyethylene composition (PE-a) further contributes to the quality of layer a and layer elements of the invention. As a result, the preferred MFR may further contribute to the quality of the layer element, and of an article comprising the layer element (preferably a PV module), if desired.
The melting temperature of the ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-b) is preferably 70 ℃ to 120 ℃, more preferably 75 ℃ to 110 ℃, further preferably 80 ℃ to 100 ℃, and most preferably 85 ℃ to 95 ℃. The preferred melting temperature is beneficial for e.g. lamination processes, as the time for the melting/softening step can be reduced.
Preferably, the ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-b) has a density of 920 to 960kg/m 3 Preferably 925 to 955kg/m 3 Most preferably 930 to 950kg/m 3 。
The ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-b) may be, for example, commercially available or may be prepared according to or analogously to known polymerization processes described in the chemical literature.
In a preferred embodiment, the copolymer of ethylene (PE-A-a) or the copolymer of ethylene (PE-A-b) is produced by: in the High Pressure (HP) process, ethylene is suitably polymerized with silane group containing comonomer units as defined above (and polar comonomer units as described above in the case of ethylene copolymers (PE-a-b)) using a free radical polymerization in the presence of one or more initiators, and optionally using Chain Transfer Agents (CTA) to control the MFR of the polymer.
Suitable High Pressure (HP) processes with suitable polymerisation conditions are described in WO 2018/141672.
This HP polymerization produces so-called low density ethylene polymers (LDPE), herein an ethylene copolymer (PE-a) or an ethylene copolymer (PE-a-b). The term LDPE has a well-known meaning in the polymer field, which describes the properties of polyethylene produced in HP, i.e. typical features distinguishing LDPE from PE, such as different branching structures; the PE is produced in the presence of an olefin polymerization catalyst (also referred to as a coordination catalyst). Although the term LDPE is an abbreviation for low density polyethylene, the term should not be understood as limiting the density range, but rather covers HP polyethylenes of the LDPE class having low, medium and higher densities.
The polyethylene composition (PE-a) preferably comprises from 20.0 wt% to 100 wt%, more preferably from 20.0 wt% to 99.9999 wt%, further preferably from 65.0 to 99.999 wt%, most preferably from 87.5 to 99.99 wt% of the ethylene copolymer (PE-a) or the ethylene copolymer (PE-a-b), relative to the total weight of the polyethylene composition (PE-a).
The amount of ethylene copolymer (PE-A-a) or ethylene copolymer (PE-B-B) in the polyethylene composition (PE-A) depends on the additional components present in the polyethylene composition (PE-A).
The polyethylene composition (PE-a) suitably comprises additives other than fillers, pigments, carbon black or flame retardants, these terms having well-known meanings in the prior art.
Optional additives are, for example, conventional additives suitable for the desired end use and within the skill of the person skilled in the art, including, but not limited to, preferably at least antioxidants, ultraviolet light stabilizers and/or ultraviolet light absorbers, and may also include metal deactivators, clarifiers, brighteners, acid scavengers, slip agents, and the like. The individual additives can be used, for example, in conventional amounts, the total amount of additives present in the PE composition (PE-A) preferably being defined as follows. Such additives are generally commercially available and are described, for example, in Hans Zweifel 2001, 5 th edition "plastics additives handbook".
The amount of additive is preferably at most 10.0 wt. -%, such as 0.0001 to 10.0 wt. -%, more preferably 0.001 to 5.0 wt. -%, most preferably 0.01 to 2.5 wt. -%, relative to the total weight of the polyethylene composition (PE-a).
The polyethylene composition (PE-a) may further comprise fillers, pigments, carbon black and/or flame retardants.
Optional fillers, pigments, carbon black or flame retardants are generally conventional and commercially available. Suitable optional fillers and pigments are as defined herein in the context of layer C for fillers, pigments. The optional carbon black may be any conventional product suitable for layer a. The optional flame retardant may be as defined in layer C or claims below, or such as magnesium hydroxide, ammonium polyphosphate, and the like.
The amount of fillers, pigments, carbon black and/or flame retardants is preferably in the range of up to 70.0 wt. -%, e.g. 0.1 to 70.0 wt. -%, preferably 0.5 to 30.0 wt. -%, most preferably 1.0 to 10.0 wt. -%, relative to the total weight of the polyethylene composition (PE-a).
The polyethylene composition (PE-A) may further comprise a polymer different from the ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-b).
However, it is preferred that the polyethylene composition (PE-A) comprises as polymer component only an ethylene copolymer (PE-A-a) or an ethylene copolymer (PE-A-b).
The "polymer component" herein does not comprise any carrier polymer, such as the carrier polymer used in an additive masterbatch, or any filler, pigment, carbon black or flame retardant, optionally, respectively, present in the polyethylene composition (PE-a), optionally additives or fillers, pigments, carbon black or flame retardants. This optional carrier polymer is calculated as the amount of the respective additive or pigment or filler, relative to the amount of the polyethylene composition (PE-a) (100 wt%).
In one embodiment, the polyethylene composition (PE-a) comprises, preferably consists of, relative to the amount of polyethylene composition (PE-a) (100 wt%):
-from 90.0 to 99.9999 wt%, preferably from 95.0 to 99.999 wt%, most preferably from 97.5 to 99.99 of an ethylene copolymer; and
-from 0.0001 to 10.0 wt.%, preferably 0.001 and 5.0 wt.%, most preferably 0.01 and 2.5 wt.% of additives.
In such embodiments, the polyethylene composition (PE-A) typically has a melt flow rate MFR in the same range as defined above for the ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-b) 2 Density, melting temperature Tm and shear thinning index SHI 0.05/300 。
In another embodiment, the polyethylene composition (PE-a) comprises one or more of a filler, a pigment, carbon black or a flame retardant in addition to suitable additives as defined above. Thus, the polyethylene composition (PE-a) comprises, preferably consists of, relative to the total amount (100 wt%) of the polyethylene composition (PE-a):
20.0 to 99.8999 wt%, preferably 65.0 to 99.499 wt%, most preferably 87.5 to 98.99 wt% of an ethylene copolymer;
-from 0.0001 to 10.0 wt.%, preferably 0.001 and 5.0 wt.%, most preferably 0.01 and 2.5 wt.% of additives; and
-0.1 to 70.0 wt%, preferably 0.5 to 30.0 wt%, most preferably 1.0 to 10.0 wt% of one or more of a filler, pigment, carbon black or flame retardant.
In yet another embodiment, the polyethylene composition (PE-a) comprises, preferably consists of, relative to the total amount (100 wt%) of the polyethylene composition (PE-a):
-80.0 to 99.9999 wt% of an ethylene copolymer;
from 0.0001 to 10.0% by weight, preferably from 0.001 and 5.0% by weight, most preferably from 0.01 and 2.5% by weight, of additives and
-0 to 20.0 wt%, preferably 0.5 to 15.0 wt%, most preferably 1.0 to 10.0 wt% of one or more of a filler or pigment; pigments are preferred.
In such embodiments, the polyethylene composition (PE-A) generally has the same definitions as for the ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-b) described aboveRange of melt flow rate MFR 2 And shear thinning index SHI 0.05/300 。
Preferably, layer a of the layer element consists of a polyethylene composition (PE-a) comprising an ethylene copolymer as defined above, below or in the claims.
Layer a, preferably a polyethylene composition (PE-a), most preferably an ethylene copolymer, is preferably not crosslinked using peroxide.
However, if desired, depending on the end application, the polyethylene composition (PE-a) may be crosslinked by silane group containing units using a Silanol Condensation Catalyst (SCC), preferably selected from carboxylates of tin, zinc, iron, lead or cobalt or aromatic organic sulfonic acids, before or during the lamination process of the layer element of the invention. Such SCCs are commercially available, for example.
It will be appreciated that SCC as defined above is that conventionally provided for cross-linking purposes.
If present, the amount of optional crosslinking agent (SCC) is preferably from 0 to 0.1 mol/kg of ethylene copolymer, for example from 0.00001 to 0.1, preferably from 0.0001 to 0.01, more preferably from 0.0002 to 0.005, more preferably from 0.0005 to 0.005 mol/kg of ethylene copolymer.
Preferably, no crosslinking agent (SCC) is present in the Layer Element (LE).
In a preferred embodiment, no Silane Condensation Catalyst (SCC) selected from tin-organic catalysts or aromatic organosulfonic acids is present in the polyethylene composition (PE-a). In a further preferred embodiment, no peroxide or Silane Condensation Catalyst (SCC) as defined above is present in the polyethylene composition (PE-a).
It is particularly preferred that the polyethylene composition is uncrosslinked.
As already mentioned, the use of a polyethylene composition (PE-a) may avoid cross-linking of layer a of the layer element, which helps to achieve a good quality of the layer element.
The thickness of layer A is preferably from 100 μm to 500. Mu.m, preferably from 150 μm to 400. Mu.m, most preferably from 200 μm to 300. Mu.m.
Layer B
Layer B comprises, preferably consists of, a polyethylene composition (PE-B).
The polyethylene composition (PE-B) comprises an ethylene copolymer selected from the group consisting of:
a density of 850kg/m 3 To 905kg/m 3 A copolymer of ethylene and comonomer units (PE-B-a) selected from one or more of α -olefins having 3 to 12 carbon atoms; or
-density of 850kg/m 3 To 905kg/m 3 A copolymer (PE-B-B) of ethylene and comonomer units selected from more than one of alpha-olefins having from 3 to 12 carbon atoms, and the copolymer (PE-B-B) additionally having silane group-containing units; or
A density of 850kg/m 3 To 905kg/m 3 And a comonomer unit selected from more than one alpha-olefin having from 3 to 12 carbon atoms, and the copolymer (PE-B-c) additionally has a functional group-containing unit derived from at least one unsaturated carboxylic acid and/or anhydride, metal salt, ester, amide or imide thereof and mixtures thereof.
All of the alternative ethylene copolymers (PE-B-a), ethylene copolymers (PE-B) and ethylene copolymers (PE-B-c) have comonomer units selected from more than one of the alpha olefins having from 3 to 12 carbon atoms.
Suitable alpha-olefins having from 3 to 12 carbon atoms include 1-butene, 1-hexene and 1-octene, preferably 1-butene or 1-octene, more preferably 1-octene.
Copolymers of ethylene and 1-octene are preferably used.
The ethylene copolymer (PE-B-B) differs from the ethylene copolymer (PE-B-a) in that it also has silane group-containing units (PE-B-B).
The silane group-containing units are preferably grafted onto the polymer backbone of the ethylene copolymer (PE-B-B).
Preferably, the silane group-containing units of the ethylene copolymer (PE-B-B) are independently the same as the silane group-containing units of the above-described ethylene copolymer (PE-A-a) or ethylene copolymer (PE-A-B).
Thus, all embodiments and amounts of silane group containing units described above in relation to the ethylene copolymer (PE-A-a) or the ethylene copolymer (PE-A-B) also apply independently to silane group containing units (PE-B-B), except that the silane group containing units are preferably grafted onto the polymer backbone of the ethylene copolymer (PE-B-B).
The ethylene copolymer (PE-B-B) is preferably a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene, to which silane group-containing units have been grafted, and most preferably a copolymer of ethylene and 1-octene, to which silane group-containing units have been grafted.
Particularly preferably, the ethylene copolymer (PE-B-B) is a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene, onto which silane group-containing units selected from vinyltrimethoxysilane, vinyldimethoxyethoxysilane, vinyltriethoxysilane, more preferably vinyltrimethoxysilane or vinyltriethoxysilane, more preferably a copolymer of ethylene and 1-octene, onto which functional group-containing units selected from vinyltrimethoxysilane, vinyldimethoxyethoxysilane, vinyltriethoxysilane, more preferably vinyltrimethoxysilane or vinyltriethoxysilane are grafted.
Most preferred is a copolymer of ethylene and 1-octene, to which vinyltrimethoxysilane has been grafted.
The ethylene copolymer (PE-B-a) is preferably a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene, most preferably a copolymer of ethylene and 1-octene.
The ethylene copolymer (PE-B-c) differs from the ethylene copolymer (PE-B-a) in that it also has functional group-containing units (PE-B-c) derived from at least one unsaturated carboxylic acid and/or anhydride, metal salt, ester, amide or imide thereof and mixtures thereof.
The functional group-containing units are preferably grafted onto the polymer backbone of the ethylene copolymer (PE-B-c).
The units containing functional groups are preferably derived from a compound selected from maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, fumaric anhydride, maleic acid, citraconic acid and mixtures thereof, preferably from maleic anhydride.
The amount of the functional group-containing unit present therein is preferably 0.01 to 1.5mol%, more preferably 0.01 to 1.00mol%, further preferably 0.02 to 0.80mol%, even more preferably 0.02 to 0.60mol%, most preferably 0.03 to 0.50mol%, relative to the total amount of the monomer units in the ethylene copolymer (PE-B-c).
The copolymer of ethylene (PE-B-c) is preferably a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene, onto which the functional group-containing unit is grafted, and most preferably a copolymer of ethylene and 1-octene, onto which the functional group-containing unit is grafted.
Particularly preferred is an ethylene copolymer (PE-B-c) which is preferably a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene having functional group-containing units grafted thereon, the functional group-containing units being derived from maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, fumaric anhydride, maleic acid, citraconic acid and mixtures thereof, more preferably maleic anhydride, still more preferably a copolymer of ethylene and 1-octene having functional group-containing units grafted thereon, the functional group-containing units being derived from maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, fumaric anhydride, maleic acid, citraconic acid and mixtures thereof, most preferably maleic anhydride.
In a preferred embodiment, the polyethylene composition (PE-B) comprises an ethylene copolymer selected from the group consisting of:
a density of 850kg/m 3 To 905kg/m 3 A copolymer of ethylene and comonomer units (PE-B-a) selected from one or more of α -olefins having 3 to 12 carbon atoms; or
A density of 850kg/m 3 To 905kg/m 3 Copolymers of ethylene and comonomer units (PE-B-B), coThe comonomer units are selected from more than one of alpha-olefins having 3 to 12 carbon atoms, and the copolymer (PE-B-B) additionally has silane group-containing units;
all alternative ethylene copolymers (PE-B-a), ethylene copolymers (PE-B-B) and ethylene copolymers (PE-B-c) are characterized by the following characteristics:
the ethylene copolymer is preferably an ethylene-based plastomer.
The density of the ethylene copolymer is 850 to 905kg/m 3 Preferably from 855 to 900kg/m 3 More preferably 860 to 895kg/m 3 Most preferably from 865 to 890kg/m 3 。
MFR of ethylene copolymer 2 Preferably less than 20g/min, more preferably less than 15g/10min, even more preferably from 0.1 to 13g/10min, still more preferably from 0.5 to 10g/10min, most preferably from 0.8 to 8.0g/10min.
The ethylene copolymer preferably has a melting temperature below 130 ℃, preferably below 120 ℃, more preferably below 110 ℃ and most preferably below 100 ℃.
Furthermore, the glass transition temperature Tg (measured according to ISO 6721-7 with DMTA) of the ethylene copolymers is preferably below-25 ℃, preferably below-30 ℃ and more preferably below-35 ℃.
The ethylene content of the ethylene copolymer is preferably from 55.0 to 95.0% by weight, preferably from 60.0 to 90.0% by weight, more preferably from 65.0 to 88.0% by weight.
The molecular weight distribution Mw/Mn of the ethylene copolymers is most often below 4.0, for example below 3.8, but at least 1.7. Preferably between 3.5 and 1.8.
The ethylene copolymer may be any ethylene copolymer having the above-mentioned properties, which is commercially available under the trade name Queo from North European chemical, under the trade name Engage or Affinity from DOW, or under the trade name Tafmer from Mitsui.
Alternatively, the ethylene copolymers may be prepared in a one-or two-step polymerization process, including solution polymerization, slurry polymerization, gas phase polymerization, or combinations thereof, by known methods in the presence of a suitable catalyst, such as a vanadia catalyst or a single-site catalyst (e.g., metallocene or constrained geometry catalyst) as known to those skilled in the art.
Suitable polymerization methods are described in WO 2019/134904.
The polyethylene composition (PE-B) preferably comprises the ethylene copolymer (PE-B-a), the ethylene copolymer (PE-B) or the ethylene copolymer (PE-B-c) in an amount of from 30.0 to 100 wt. -%, more preferably from 30.0 to 99.9999 wt. -%, still more preferably from 40.0 to 99.999 wt. -%, most preferably from 50.0 to 99.99 wt. -%, relative to the total weight of the polyethylene composition (PE-B).
The amount of ethylene copolymer (PE-B-a), ethylene copolymer (PE-B-B) or ethylene copolymer (PE-B-c) in the polyethylene composition (PE-B) depends on the additional components in the polyethylene composition (PE-B).
The polyethylene composition (PE-B) suitably comprises additives other than fillers, pigments, carbon black or flame retardants, these terms having well-known meanings in the prior art.
Preferably, the optional additives are independently selected from the list and amounts of additives for polyethylene compositions (PE-a) as described above.
The polyethylene composition (PE-B) may further comprise pigments, carbon black and/or flame retardants.
The optional pigment, carbon black or flame retardant is preferably independently selected from the group of pigments, carbon blacks or flame retardants for polyethylene compositions (PE-a) as described above and with reference to the list of additives for layer C.
The amount of pigment, carbon black and/or flame retardant is preferably at most 40.0 wt. -%, e.g. 0.1 to 40.0 wt. -%, preferably 0.5 to 30.0 wt. -%, most preferably 1.0 to 15.0 wt. -%, relative to the total weight of the polyethylene composition (PE-B).
The polyethylene composition (PE-B) may further comprise a polymer different from the ethylene copolymer (PE-B-a), the ethylene copolymer (PE-B-B) or the ethylene copolymer (PE-B-c).
The optional polymer is preferably selected from propylene-based polymers or ethylene-based polymers or mixtures thereof.
The optional propylene-based polymer is preferably selected from the group consisting of propylene-alpha-olefin random copolymers and heterophasic propylene copolymers or mixtures thereof.
The optional ethylene-based polymer is preferably selected from ethylene-alpha-olefin copolymers or mixtures thereof.
The amount of polymer different from the ethylene copolymer (PE-B-a), the ethylene copolymer (PE-B) or the ethylene copolymer (PE-B-c) is preferably at most 60.0 wt. -%, e.g. 2.0 to 60.0 wt. -%, preferably 5.0 to 50.0 wt. -%, most preferably 10 to 40.0 wt. -%, relative to the total weight of the polyethylene composition (PE-B).
The polyethylene composition (PE-B) preferably does not contain fillers as defined above or below for layer a and layer C.
In one embodiment, the polyethylene composition (PE-B) comprises, preferably consists of, relative to the amount of polyethylene composition (PE-B) (100 wt%):
-from 90.0 to 99.9999 wt%, preferably from 95.0 to 99.999 wt%, most preferably from 97.5 to 99.99 wt% of an ethylene copolymer; and
-from 0.0001 to 10.0 wt.%, preferably 0.001 and 5.0 wt.%, most preferably 0.01 and 2.5 wt.% of additives.
In such embodiments, the polyethylene composition (PE-B) will generally have an MFR in the same range as defined above for the ethylene copolymer (PE-B-a), the ethylene copolymer (PE-B-B) or the ethylene copolymer (PE-B-c) 2 Density, melting temperature Tm and glass transition temperature Tg properties.
In another embodiment, the polyethylene composition (PE-B) comprises one or more of the pigments, carbon black or flame retardants as defined above in addition to suitable additives as defined above. Thus, the polyethylene composition (PE-B) comprises, preferably consists of, relative to the total amount (100 wt%) of the polyethylene composition (PE-B):
-from 40.0 to 99.8999 wt%, preferably from 65.0 to 99.499 wt%, most preferably from 87.5 to 98.99 wt% of an ethylene copolymer;
-from 0.0001 to 10.0 wt.%, preferably from 0.001 to 5.0 wt.%, most preferably from 0.01 and 2.5 wt.% of additives; and
-0.1 to 40.0 wt%, preferably 0.5 to 30.0 wt%, most preferably 1.0 to 15.0 wt% of one or more of a pigment, carbon black or flame retardant.
In yet another embodiment, the polyethylene composition (PE-B) comprises the additive as defined above and one or more polymers different from the ethylene copolymer (PE-B-a), the ethylene copolymer (PE-B) or the ethylene copolymer (PE-B-c) as defined above. Thus, the polyethylene composition (PE-B) comprises, preferably consists of, relative to the total amount (100 wt%) of the polyethylene composition (PE-B):
-from 40.0 to 99.8999 wt%, preferably from 50.0 to 99.0 wt%, most preferably from 60.0 to 98.5 wt% of an ethylene copolymer;
-from 0.0001 to 10.0 wt.%, preferably 0.001 and 5.0 wt.%, most preferably 0.01 and 2.5 wt.% of additives; and
-2.0 to 60.0 wt.%, preferably 5.0 to 50.0 wt.%, most preferably 10.0 to 40.0 wt.% of one or more different polymers.
In yet another embodiment, the polyethylene composition (PE-B) comprises, in addition to suitable additives as defined above, one or more polymers other than ethylene copolymer (PE-B-a), ethylene copolymer (PE-B) or ethylene copolymer (PE-B-c) and one or more pigments, carbon black or flame retardants as defined above. Thus, the polyethylene composition (PE-B) comprises, preferably consists of, relative to the total amount (100 wt%) of the polyethylene composition (PE-B):
-from 30.0 to 99.8999 wt%, preferably from 40.0 to 99.0 wt%, most preferably from 50.0 to 98.5 wt% of an ethylene copolymer;
-from 0.0001 to 10.0 wt.%, preferably 0.001 and 5.0 wt.%, most preferably 0.01 and 2.5 wt.% of additives;
-from 2.0 to 60.0 wt.%, preferably from 5.0 to 50.0 wt.%, most preferably from 10.0 to 40.0 wt.% of one or more different polymers, and
-0.1 to 40.0 wt%, preferably 0.5 to 30.0 wt%, most preferably 1.0 to 15.0 wt% of one or more of a pigment, carbon black or flame retardant.
In the presence of more than one different polymer, the properties of the polyethylene composition (PE-B) are generally influenced not only by the properties of the ethylene copolymer, but also by the properties of more than one different polymer. Thus, the properties of the polyethylene composition may differ from those of the ethylene copolymer (PE-B-a), the ethylene copolymer (PE-B-B) or the ethylene copolymer (PE-B-c).
Preferably, layer B of the layer element consists of a polyethylene composition (PE-B) comprising an ethylene copolymer as defined above, below or in the claims.
The thickness of layer B is preferably from 50 μm to 500. Mu.m, preferably from 75 μm to 400. Mu.m, most preferably from 100 μm to 300. Mu.m.
Layer C
Layer C comprises, preferably consists of, a polypropylene composition (PP-C).
The polypropylene composition (PP-C) comprises a propylene polymer (PP-C-a).
The propylene polymer (PP-C-a) may be a single propylene polymer or a mixture of two or more different propylene polymers.
The propylene polymer (PP-C-a) may be a propylene homopolymer or a propylene copolymer.
Preferably, the propylene polymer (PP-C-a) is at least a propylene copolymer. More preferably, the propylene polymer (PP-C-a) is at least one (preferably one) heterophasic propylene copolymer comprising, preferably consisting of:
a polypropylene matrix component, and
an elastomeric propylene copolymer component dispersed in the polypropylene matrix; or
Mixtures of more than two, for example two, different heterophasic propylene copolymers.
The heterophasic propylene copolymer preferably has one or more of the following properties:
-a melting temperature Tm of at least 145 ℃, preferably 155 to 175 ℃, most preferably 160 to 170 ℃;
-a Vicat softening temperature Vicat a of at least 90 ℃, preferably 105 to 165 ℃, most preferably 110 to 155 ℃;
melt flow Rate MFR 2 Is 1.0 to 20.0g/10min, preferably 2.0 to 18g/10min, preferably 3.0 to 15.0 g-10min；
-the amount of Xylene Cold Soluble (XCS) fraction is from 5 to 40 wt. -%, preferably from 10 to 35 wt. -%;
-comonomer content from 2.0.0 to 20.0 wt%, preferably from 3.0 to 18 wt%;
-a flexural modulus of at least 600MPa, preferably 750 to 2500MPa; and/or
A density of 900 to 910kg/m 3 。
Preferably the heterophasic propylene copolymer has all of the above mentioned properties.
Preferably, the polypropylene composition (PP-C) comprises, with respect to the total amount of the polypropylene composition (100 wt%):
-5 to 50 wt% of a heterophasic propylene copolymer (PP-C-a) having a melting temperature (Tm) of at least 145 ℃ and a Vicat softening temperature (Vicat a) of at least 90 ℃ and comprising a polypropylene matrix component (a 1) and an elastomeric propylene copolymer component (a 2) dispersed in said polypropylene matrix (a 1), when measured according to the following determination methods, and
-20 to 60 wt% of a heterophasic propylene copolymer (PP-C-b) having a melting temperature (Tm) of at least 145 ℃, a Vicat softening temperature (Vicat A) of at least 90 ℃ and comprising a polypropylene matrix component (b 1) and an elastomeric propylene copolymer component (b 2) dispersed in the polypropylene matrix (b 1), when measured according to the following determination methods,
-10 to 40% by weight of an inorganic filler,
-from 0 to 35% by weight of a pigment,
-0 to 30% by weight of a plastomer, and
-0.3 to 5% by weight of additives other than inorganic fillers;
wherein the amount of Xylene Cold Soluble (XCS) fraction of the heterophasic propylene copolymer (PP-C-b) is higher than the amount of Xylene Cold Soluble (XCS) fraction of the heterophasic propylene copolymer (PP-C-a).
The polypropylene matrix component of the heterophasic propylene copolymer (PP-C-a) may be a propylene homopolymer component or a propylene random copolymer component, preferably a propylene homopolymer component.
The heterophasic propylene copolymer (PP-C-a) preferably has one or more, more preferably all of the following properties:
-MFR 2 from 0.2 to 15.0g/10min, more preferably from 0.5 to 10g/10min, most preferably from 1.0 to 7.0g/10min,
-the amount of Xylene Cold Soluble (XCS) fraction is from 3 to 30 wt. -%, more preferably from 5 to 25 wt. -%, still more preferably from 5 to 20 wt. -%, most preferably from 8 to 17 wt. -%,
-a comonomer content of from 0.5 to 20 wt.%, more preferably from 1.0 to 20 wt.%, still more preferably from 1.2 to 10 wt.%, even more preferably from 2.0 to 10 wt.%, most preferably from 2.0 to 8.0 wt.%, whereby preferred comonomers are selected from ethylene and/or C4-C8 alpha olefin comonomers, more preferably ethylene,
a melting temperature Tm of 158 to 170 ℃, more preferably 160 to 170 ℃, still preferably 163 to 170 ℃, most preferably 163 to 167 ℃,
a flexural modulus of at least 900MPa, more preferably of from 950 to 3000MPa, still more preferably of from 1000 to 2400MPa, even more preferably of from 1100 to 2300MPa, most preferably of from 1200 to 2200MPa,
a density of 900 to 910kg/m 3 And/or
-a Vicat softening temperature (Vicat a) of at least 100 ℃, more preferably from 130 to 200 ℃, still more preferably from 145 to 165 ℃, most preferably from 148 to 165 ℃.
In a preferred embodiment the heterophasic propylene copolymer (PP-C-a) fulfils all the above comonomer contents, tm, vicat A, MFR 2 XCS fraction, flexural modulus and density.
The polypropylene matrix component of the heterophasic propylene copolymer (PP-C-b) may be a propylene homopolymer component or a propylene random copolymer component, preferably a propylene homopolymer component.
The heterophasic propylene copolymer (PP-C-b) preferably has one or more, more preferably all of the following properties:
-MFR 2 from 3.0 to 25.0g/10min, more preferably from 5.0 to 20g/10min, most preferably from 7.0 to 18g/10min,
-the amount of Xylene Cold Soluble (XCS) fraction is from 10 to 60 wt. -%, more preferably from 15 to 50 wt. -%, still more preferably from 15 to 40 wt. -%, most preferably from 20 to 37 wt. -%,
a comonomer content of from 5.0 to 35 wt.%, more preferably from 5.0 to 30 wt.%, still more preferably from 7.0 to 25 wt.%, most preferably from 10 to 20 wt.%, whereby preferred comonomers are selected from ethylene and/or C4-C8 alpha olefin comonomers, more preferably ethylene,
-a melting temperature Tm of 158 to 170 ℃, more preferably 160 to 170 ℃, most preferably 163 to 167 ℃,
-flexural modulus of less than 1000MPa, more preferably from 300 to 950MPa, still more preferably from 400 to 900MPa, even more preferably from 500 to 900MPa, most preferably from 550 to 850MPa,
a density of 900 to 910kg/m 3 And/or
-a Vicat softening temperature (Vicat a) of at least 90 ℃, more preferably from 100 to 200 ℃, still more preferably from 105 to 150 ℃, most preferably from 110 to 145 ℃.
According to yet another preferred embodiment, the polypropylene composition (PP-C) comprises, relative to the total amount of the polypropylene composition (100 wt%):
-5 to 50 wt% of a heterophasic propylene copolymer (PP-C-a) having a melting temperature (Tm) of at least 145 ℃ (DSC), a Vicat softening temperature (Vicat a) of at least 90 ℃ (according to ASTM D1525, method a,50 ℃/h, 10N) when measured according to the determination method described below, and comprising a polypropylene matrix component (a 1) and an elastomeric propylene copolymer component (a 2) dispersed in said polypropylene matrix (a 1), and
-20 to 60 wt% of a heterophasic propylene copolymer (PP-C-b) having a melting temperature (Tm) of at least 145 ℃ (DSC), a Vicat softening temperature (Vicat a) of at least 90 ℃ (according to ASTM D1525, method a,50 ℃/h, 10N) and comprising a polypropylene matrix component (b 1) and an elastomeric propylene copolymer component (b 2) dispersed in said polypropylene matrix (b 1), when measured according to the determination method described below, and
-5 to 30% by weight of an inorganic filler,
-from 0 to 35% by weight of a pigment,
0 to 30% by weight of a plastomer, and
-from 0.3 to 5% by weight of additives other than inorganic fillers;
wherein the amount of Xylene Cold Soluble (XCS) fraction of the heterophasic propylene copolymer (PP-C-b) is higher than the amount of Xylene Cold Soluble (XCS) fraction of the heterophasic propylene copolymer (PP-C-a).
In a preferred embodiment the heterophasic propylene copolymer (PP-C-b) fulfils all the above comonomer contents, tm, vicat A, MFR 2 XCS fraction, flexural modulus and density.
Heterophasic propylene copolymers (PP-C-b) differ from heterophasic propylene copolymers (PP-C-a) typically by a higher amount of Xylene Cold Soluble (XCS) fraction.
Further, the heterophasic propylene copolymer (PP-C-b) preferably has a higher MFR than the heterophasic propylene copolymer (PP-C-a) 2 。
Furthermore, the heterophasic propylene copolymer (PP-C-b) preferably has a higher elastomeric phase content than the heterophasic propylene copolymer (PP-C-a).
Furthermore, the heterophasic propylene copolymer (PP-C-b) preferably has a higher comonomer content than the heterophasic propylene copolymer (PP-C-a).
Furthermore, the heterophasic propylene copolymer (PP-C-b) preferably has a lower flexural modulus than the heterophasic propylene copolymer (PP-C-a).
The propylene polymer (PP-C-a), preferably a heterophasic propylene copolymer, may be of a commercially available brand or may be produced, e.g. by conventional polymerization processes and process conditions, e.g. using conventional catalyst systems known in the literature.
The propylene polymer (PP-C-a), preferably a heterophasic propylene copolymer as described herein, may be polymerized in a sequential polymerization process, e.g. a multistage process.
Suitable methods are described in WO 2017/071847.
A preferred multistage process is the "loop-gas phase" process, such as developed by the chemical company Nordic Denmark (known as
Techniques) described, for example, in the patent literature, e.g. EP 0887379. WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315.
Another suitable slurry-gas phase process is that of LyondellBasell
And (5) processing.
After the propylene polymer (PP-C-a) has been removed from the final polymerization stage, it is preferably subjected to a process step for removing residual hydrocarbons from the polymer. Such processes are well known in the art and may include a depressurization step, a purge step, a stripping step, an extraction step, and the like. Combinations of different steps are also possible. After removal of residual hydrocarbons, the heterophasic propylene copolymer is preferably mixed with additives, as is well known in the art. Such additives are described above for the polypropylene composition (PP-C). The polymer particles are then extruded into pellets as is well known in the art. Preferably, the extruding step uses a co-rotating twin screw extruder. Such extruders are manufactured, for example, by Coperion (Werner & Pfleiderer) and Japan Steel Works.
The propylene polymer (PP-C-a) is preferably produced by polymerisation using any suitable type of Ziegler-Natta. Typical suitable ziegler-natta type catalysts are stereospecific (stereospecific) high yield solid ziegler-natta catalyst components comprising Mg, ti and Cl as essential components. In addition to solid catalysts, polymerization processes typically employ a cocatalyst in conjunction with an external donor.
The catalyst ingredients may be supported on a particulate support, for example an inorganic oxide such as silica or alumina, or a solid support is typically formed using a magnesium halide. The catalyst component may be prepared by an emulsion solidification method or a precipitation method, instead of being supported on an external carrier.
Alternatively, the propylene polymer (PP-C-a) of the present invention may be produced using a modified catalyst system as described below.
More preferably, the vinyl compounds of formula (I) are used for the modification of catalysts:
CH 2 ＝CH–CHR 1 R 2 (IV)
in the formula, R 1 And R 2 Together form a five-or six-membered saturated, unsaturated or aromatic ring, optionally containing substituents, or independently represent an alkyl group containing 1 to 4 carbon atoms, wherein at R 1 And R 2 In the case of aromatic ring formation, -CHR 1 R 2 Hydrogen atoms are partly absent.
More preferably, vinyl compound (IV) is selected from: vinylcycloalkanes, preferably Vinylcyclohexane (VCH), vinylcyclopentane, 3-methyl-1-butene polymers and vinyl-2-methylcyclohexane polymers. Most preferably, vinyl compound (IV) is a Vinylcyclohexane (VCH) polymer.
The solid catalyst also typically comprises an electron donor (internal electron donor) and optionally aluminum. Suitable internal electron donors are, in particular, esters of carboxylic or dicarboxylic acids, such as phthalates, maleates, benzoates, citraconates and succinates, 1, 3-diethers or oxygen-or nitrogen-containing silicon compounds. Furthermore, mixtures of donors may be used.
The cocatalyst generally comprises an alkylaluminum compound. The aluminum alkyl compound is preferably an aluminum trialkyl, such as trimethylaluminum, triethylaluminum, triisobutylaluminum or tri-n-octylaluminum. However, it may also be an alkylaluminum halide, such as diethylaluminum chloride, dimethylaluminum chloride and sesquiethylaluminum chloride.
Suitable external electron donors for polymerization are well known in the art and include ethers, ketones, amines, alcohols, phenols, phosphines, and silanes. The silane type external donors are generally Si-OCOR, si-OR OR Si-NR containing silicon as central atom, as is known in the art 2 A bonded organosilane compound wherein R is an alkyl, alkenyl, aryl, aralkyl or cycloalkyl group of 1 to 20 carbon atoms.
Examples of suitable catalysts and compounds in catalysts are described in, inter alia, WO 87/07620, WO 92/21705, WO 93/11165, WO 93/11166, WO 93/19100, WO 97/36939, WO 98/12234, WO 99/33842, WO 03/000756, WO 03/000757, WO 03/000754, WO 03/000755, WO 2004/029112, EP 2611, WO 2012/007430, WO 92/19659, WO 92/19653, WO 92/19658, US 4382019, US 4435550, US 4465782, US 4473660, US 4560671, US 5539067, US 565671, EP 18775, EP 18776, EP45977, WO 45995/32994, US 4107414, US 4107, US 4226963, US 4347160, US 447272524, US 4522930, US 453246313, US 4546882, US 57882.
The polypropylene composition (PP-C) preferably comprises additives.
Herein, the term "additive" does not comprise optional fillers, optional pigments and optional flame retardants. Such additives are preferably conventional and commercially available and include, but are not limited to, UV stabilizers, antioxidants, nucleating agents, clarifiers, brighteners, acid scavengers, as well as slip agents, processing aids, and the like. Such additives are generally commercially available and are described, for example, in the "plastics additives handbook" of 5 th edition of Hans Zweifel 2001.
Each additive may be used, for example, in conventional amounts. The skilled artisan can select suitable additives and amounts thereof for layer C depending on the desired article and its end use.
Preferably, the additive is selected from at least a UV stabilizer comprising a hindered amine compound and an antioxidant comprising a dialkylamine compound. More preferably, the additive is at least selected from the group consisting of a UV stabilizer comprising a hindered amine compound and an antioxidant comprising a dialkylamine compound, and wherein the additive is free of phenolic units. The expression "the additive does not contain phenolic units" means herein that any additive compound present in the polypropylene composition (PP-C), including UV stabilizers and antioxidants, does not contain phenolic units. Preferably, the composition does not contain any ingredients with phenolic units, such as additives.
Thus, fillers, pigments and flame retardants are not understood or defined herein as additives.
Preferably, the polypropylene composition (PP-C) comprises additives and/or at least one or two selected from the group of more than one of fillers, pigments and flame retardants.
If present, the optional filler is preferably an inorganic filler, more preferably a single inorganic filler. The particle size and/or aspect ratio of the filler may be varied as is well known to the skilled person. Preferably, the filler is selected from one or more of wollastonite, talc or glass fiber. Such filler products are commercial products having different particle sizes and/or aspect ratios, and may be selected by the skilled artisan according to the desired end product and end application. The fillers may be, for example, conventional and commercially available. The amount of filler, if present, is preferably from 10 to 40 wt. -%, preferably from 15 to 30 wt. -%, relative to the total amount (100 wt%) of the polypropylene composition (PP-C).
If present, the optional pigment is preferably selected from wollastonite, mica, titanium dioxide TiO 2 Talc, caCO 3 And dolomite.
Preferably the pigment is a white pigment. The white pigment is preferably TiO 2 . Such pigments are known, for example, as commercially available TiO 2 Pigment obtained, also referred to herein as TiO 2 . Any carrier medium, such as a carrier polymer, takes into account the amount of pigment. The amount of pigment (if present) is preferably from 2 to 35 wt%, preferably from 3 to 30 wt%, preferably from 5 to 25 wt%, relative to the total amount of the polypropylene composition (PP-C).
It should be noted that wollastonite and talc may be used as both fillers and pigments. When they act as pigments, they are generally present in an amount of from 2 to less than 15% by weight, preferably from 3 to 10% by weight, relative to the total amount of the polypropylene composition (PP-C). When they act as fillers, they are generally present in an amount ranging from 15 to 40% by weight, preferably from 20 to 30% by weight, with respect to the total amount of the polypropylene composition (PP-C).
If present, the optional flame retardant may be, for example, any commercial flame retardant product, preferably a flame retardant comprising inorganic phosphorus. The amount of flame retardant, if present, is preferably from 1 to 20 wt%, preferably from 2 to 15 wt%, more preferably from 3 to 12 wt%, relative to the amount of the polypropylene composition (PP-C).
Any optional carrier polymer of additives, optional fillers, optional pigments and optional flame retardants, e.g. a masterbatch of said ingredients, is included together with the carrier polymer in the amount of the respective ingredient relative to the amount of the polypropylene composition (PP-C) (100%).
In one embodiment, the PP composition comprises at least a pigment.
The optional further polymer component may be any polymer other than the propylene polymer (PP-C-a), preferably a polyolefin-based polymer. Typical examples of other polymer components are one or both of plastomers or functionalized polymers, all of which have well known meanings.
If present, the optional plastomer is preferably a copolymer of ethylene and at least one C3 to C10 alpha-olefin. The plastomer (if present) preferably has one or all, preferably all, of the following properties:
-a density of 850 to 915kg/m 3 Preferably 860 to 910kg/m 3 ，
-MFR 2 Is 0.1 to 50, preferably 0.2 to 40g/10min (190 ℃,2.16 kg), and/or
-the alpha-olefin comonomer is octene.
If a plastomer is present, the optional plastomer is preferably produced using a metallocene catalyst, which term has a well-known meaning in the art. Suitable plastomers are commercially available, for example under the trade name QUEO supplied by Nordic chemical TM Or Engage supplied by exxonmobil TM Lucene supplied by LG, or Tafmer plastomer products supplied by Mitsui. If present, the amount of optional plastomer is lower than the amount of propylene polymer (PP-C-a).
If present, the functionalized polymer may optionally be a polymer that is functionalized, for example by grafting. For example, polar functional groups such as Maleic Anhydride (MAH), which can be grafted onto the polyolefin to form a functional polymer thereof. The propylene polymer (PP-C-a), preferably both the heterophasic propylene copolymer (PP-C-a) and the heterophasic propylene copolymer (PP-C-b), differ from the optional functionalized polymer. The propylene polymer (PP-C-a), preferably both the heterophasic propylene copolymer (PP-C-a) and the heterophasic propylene copolymer (PP-C-b), is free of grafted functional units. I.e. the term propylene polymer (PP-C-a), preferably both heterophasic propylene copolymer (PP-C-a) and heterophasic propylene copolymer (PP-C-b), does not include propylene polymers having grafted functional groups. The amount of the optional functionalized polymer, if present, is preferably from 3 to 30 wt%, preferably from 3 to 20 wt%, preferably from 3 to 18 wt%, more preferably from 4 to 15 wt%, relative to the amount of the polypropylene composition (PP-C). If present, the amount of the optional functionalized polymer is less than the amount of the propylene polymer (PP-C-a), preferably less than the amount of both the heterophasic propylene copolymer (PP-C-a) and the heterophasic propylene copolymer (PP-C-b).
Relative to the total amount of the polypropylene composition (100 wt%). The polypropylene composition (PP-C) preferably comprises:
-5 to 50 wt. -%, more preferably 10 to 40 wt. -%, still more preferably 15 to 35 wt. -%, most preferably 20 to 33 wt. -% of the heterophasic propylene copolymer (PP-C-a),
-from 25 to 70 wt. -%, more preferably from 30 to 70 wt. -%, still more preferably from 35 to 65 wt. -%, most preferably from 35 to 45 wt. -% of a heterophasic propylene copolymer (PP-C-b),
10 to 40 wt%, more preferably 10 to 35 wt%, still more preferably 15 to 30 wt%, most preferably 17 to 30 wt% of an inorganic filler,
-from 0 to 35% by weight of a pigment,
0 to 30% by weight of a plastomer, and
-from 0.3 to 5.0 wt%, more preferably from 0.5 to 3.0 wt% of additives, preferably comprising at least an antioxidant and a UV stabilizer.
In case the polypropylene composition (PP-C) comprises a plastomer, the amount of plastomer is preferably from 3 to 20 wt. -%, more preferably from 4 to 17 wt. -%, more preferably from 4 to 15 wt. -%, relative to the total amount (100 wt%) of the polypropylene composition (PP-C).
MFR of the Polypropylene composition (PP-C) 2 (230 ℃,2.16 kg) is preferably 1.0 to 25.0g/10min, more preferably 2.0 to 20g/10min, still more preferably 3.0 to 15g/10min, and most preferably 4.0 to 10g/10min.
The polypropylene composition (PP-C) according to the invention preferably has a Xylene Cold Soluble (XCS) content of from 10 to 40 wt. -%, more preferably of from 15 to 35 wt. -%, most preferably of from 15 to 30 wt. -%, relative to the total amount of the polypropylene composition (PP-C).
The Vicat softening temperature (Vicat A) of the polypropylene composition (PP-C) is preferably from 110 to 155 ℃, more preferably from 110 to 150 ℃ and most preferably from 120 to 150 ℃.
The tensile modulus of the polypropylene composition (PP-C) is preferably at least 900MPa, more preferably from 900 to 3000MPa, even more preferably from 1000 to 2700MPa, most preferably from 1200 to 2500MPa.
The polypropylene composition (PP-C) preferably has a tensile strain at break of 100 to 700%, more preferably 100 to 600%, most preferably 100 to 500%.
The polypropylene composition (PP-C) preferably has a tensile modulus of at least 800MPa, more preferably 850 to 2000MPa, when measured in the machine direction from a 200 μm monolayer cast film.
The polypropylene composition (PP-C) preferably has a tensile strain at break of 100 to 700%, more preferably at least 620%, more preferably 630 to 1500%, most preferably 650 to 1200%, when measured from a 200 μm monolayer cast film.
The obtained propylene polymer (PP-C-a), preferably both the heterophasic propylene copolymer (PP-C-a) and the heterophasic propylene copolymer (PP-C-b), is then compounded together with the additives and one or more optional ingredients as described above in a well known manner. Compounding can be carried out in a conventional extruder, such as the extruders described above. The resulting molten mixture is formed into an article or, preferably, pelletized prior to use in end applications. Some or all of the additives or optional ingredients may be added during the compounding step.
Method for producing a layer element
The invention further provides a method for producing a layer element as defined above or below, wherein the method comprises the following steps:
-bonding together the layers a, B and C of the layer element in a configuration a-B-C by extrusion or lamination; and
-recovering the formed layer element.
In one embodiment, the layers a, B and C of the layer element are produced by extrusion, preferably by coextrusion.
The term "extruded" means herein that at least two layers of a layer element may be extruded in different steps or in the same extrusion step as is well known in the art. One and preferred embodiment of an "extrusion" process for producing a layer element of at least three layers is a coextrusion process. The term "co-extrusion" means herein that at least two, preferably at least three layers a, B and C of the layer element may be co-extruded in one and the same extrusion step as is well known in the art. The term "co-extrusion" means herein that in addition to the at least three layers a, B and C, all or part of the additional layers (if present) of the layer element as described above may also be formed simultaneously using more than one extrusion head.
The extrusion step and the preferred co-extrusion step may be performed, for example, using a blown film or cast film extrusion process. Both methods have well known meanings and are described in detail in the literature in the field.
Furthermore, the extrusion step and the preferred co-extrusion step may be carried out in any conventional film extruder, preferably in a conventional cast film extruder, for example in a single or twin screw extruder. Extruder apparatus, such as cast film extruder apparatus, are described in detail in the literature and are commercially available.
Other suitable extrusion techniques suitable for producing the layer element of the present invention are, for example, blown film extrusion, such as blown film coextrusion, and extrusion processes with subsequent calendering processes, such as cast film extrusion processes, preferably cast film coextrusion processes. These techniques are well known in the art.
The extrusion conditions depend on the layer material chosen and can be chosen by the skilled person.
Preferably, the extrusion (preferably coextrusion) of the layer element is performed by cast film extrusion (preferably coextrusion by cast film coextrusion).
In extruded embodiments, with the adhesive layer between the adhesive sides of the first and second layers, the adhesive layer is typically extruded or coextruded during the extrusion steps of the first and second layers.
A portion or all of the optional additional layers of the layer element may be extruded (e.g., coextruded) onto the side of layer a or layer C (or both layers a and C) opposite the side in adhesive contact with layer B. The extrusion of the optional additional layer may be performed during the extrusion (preferably co-extrusion) step of layers a and C. Alternatively or additionally, some or all of the optional additional layers may be laminated to the opposite side of one or both of layers a and C after the extrusion (preferably coextrusion) step of layers a, B and C.
In an alternative embodiment, the layer element is manufactured by laminating at least two of the layers a, B and C to adhesive contact. Lamination is performed in a conventional lamination process using conventional lamination equipment well known in the art. In a typical lamination process, layers of layer elements formed separately are arranged to form a layer element assembly; the assembly of layer elements is then subjected to a heating step, typically under vacuum conditions, in a lamination chamber; thereafter, the layer member assembly is subjected to a pressing step under heating to build up pressure on the layer member assembly and to maintain the pressure to initiate lamination of the assembly; and subsequently subjecting the layer element to a recovery step to cool and remove the obtained layer element.
Similarly, in alternative lamination embodiments, in addition to layers a, B, and C, the layer element may include additional layers on the side opposite the adhesive side of one or both of layers a and C. In this case, some or all of the optional additional layers of the layer element may be laminated and/or extruded on the side of layer a or layer C (or both layers a and C) opposite to the side in adhesive contact with layer B. The extrusion of the optional additional layer may be performed prior to the lamination step of at least two of layers a, B and C. The lamination of the optional additional layers may be performed in a step prior to the lamination step of at least two of the layers a, B and C, during the lamination step of at least two of the layers a, B and C, or after the lamination step of at least two of the layers a, B and C.
In an alternative embodiment, in which at least two of layers a, B and C are produced by lamination, layer B is then applied on the surface of layer a or on the surface of layer C using known techniques.
For example, the formed layer element may be further treated, if desired, to improve the adhesion of the layer element or to modify the outer surface of the layer element. For example, the outer side of layers a and C (as opposed to the "adhesive" side), or in the case of producing a layer element by lamination, the "adhesive" side of the laminated layers may also be surface treated using conventional techniques and equipment well known to the skilled person.
The most preferred method of producing the layer element of the invention is the extrusion process, preferably the co-extrusion process. More preferably, the extrusion process for producing the layer element is a cast film extrusion process, most preferably a cast film co-extrusion process.
Thus, a preferred method for producing the layer element according to the invention is an extrusion method, preferably a coextrusion method, comprising the following steps:
-mixing, preferably separately melting in separate extruders, the polyethylene composition of the blend layer a (PE-a), the polyethylene composition of layer B (PE-B) and the polypropylene composition of layer C (PP-C) in separate mixing devices;
-applying (preferably simultaneously) a molten mixture of the polyethylene composition of layer a (PE-a), the polyethylene composition of layer B (PE-B) and the polypropylene composition of layer C (PP-C) through a mould, forming at least layers a, B and C of the layer element configured as a-B-C, wherein layer a and layer B, and layer B and layer C are in adhesive contact with each other;
-recovering the obtained layer element.
It is well known to apply a molten mixture of a polymer composition or its ingredients to form a layer. Melt mixing refers herein to mixing above the melting or softening point of at least the major polymeric components of the resulting mixture and is carried out, for example, but not limited to, at a temperature at least 10 to 15 ℃ above the melting or softening point of the polymeric components. The mixing step may be carried out in an extruder, such as a film extruder, for example a cast film extruder. The melt mixing step may comprise a separate mixing step in a separate mixer, such as a kneader, which is connected to and located before the extruder of the layer element production line. Mixing in the aforementioned separate mixers may be carried out by mixing with or without external heating of the ingredients (heating with an external source).
Among the above preferred processes, the extrusion process is preferably a cast film extrusion process, preferably a cast film coextrusion process. The extrusion process may also be a blown film extrusion process, preferably a blown film coextrusion process, or an extrusion process with subsequent calendering methods, such as a cast film extrusion process, preferably a cast film coextrusion process.
As mentioned above, the extrusion process for forming the layer element of the present invention may further comprise further steps after extrusion, such as further processing steps or lamination steps, preferably after the extrusion step as described above.
Article of manufacture
The article comprising the layer element may be any article in which the properties of the layer element of the invention are, for example, desirable or feasible.
The layer element may be part of or form an article, such as a film.
As non-limiting examples of such articles, there may be extruded articles or molded articles or combinations thereof. For example, the molded articles can be used in packaging (including boxes, cases, containers, bottles, and the like), household applications, vehicle parts, buildings, and any type of electronic equipment. The extruded article may be, for example, a different type of film for any purpose comprising a layer element, such as a plastic bag or a package, e.g. a wrapping paper, a shrink film, etc.; any type of electronic device; piping, etc. A combination of a moulded article and an extruded article, such as a moulded container or a bottle comprising an extruded label, the label comprising a layer element.
In one embodiment, the article is a multilayer film comprising, preferably consisting of, layer elements. In this embodiment, the layer element of the article is preferably a film for various end-use applications, such as, but not limited to, packaging applications. In the present invention, the term "film" also covers thicker sheet structures, for example for thermoforming.
In a second embodiment, the article is an assembly comprising two or more layer elements, wherein at least one layer element is a layer element of the present invention. The other layer elements of the assembly may be different or identical to the layer elements of the invention.
The second embodiment is a preferred embodiment of the present invention.
The preferred assembly of the second embodiment is preferably a Photovoltaic (PV) module comprising a photovoltaic element and one or more further layer elements, wherein at least one layer element is a layer element of the invention.
A preferred Photovoltaic (PV) module of the invention comprises, in the given order, a protective front layer element, preferably a glass layer element, a front encapsulation layer element, a photovoltaic element and a Layer Element (LE) of the invention.
In this preferred embodiment, the layer element of the invention is multifunctional, i.e. it serves both as a rear encapsulation layer element and as a protective backing layer element. More preferably, layer a serves as an encapsulation layer element and layer C serves as a protective backing layer element, also referred to herein as a backsheet layer element. Layer B acts as an adhesive layer to improve the adhesion between the encapsulation layer element and the protective backing layer element. Naturally, as described above in the "Layer Element (LE) of the invention", the outer surface of layer a may have additional layers attached to enhance the function of the "encapsulation layer element". More naturally, the outer surface of layer C may have additional layers attached to enhance the function of the "protective backing layer element". Such additional layers may be introduced separately to layer a and layer C in any order by extrusion, such as coextrusion, or by lamination, or by a combination thereof.
In a preferred Photovoltaic (PV) module of the invention, the side of layer a opposite the side to which layer B is adhered is preferably in adhesive contact with the photovoltaic element of the PV module.
In addition, the side of layer C opposite the side to which layer B is adhered may be in adhesive contact with other layers or layer elements, as is known in the art of backsheet layer elements for PV modules.
The finished photovoltaic module may be rigid or flexible.
Furthermore, the finished PV module of the invention can be arranged, for example, onto a metal (e.g., aluminum) frame.
All such terms have well-known meanings in the art.
The materials for the above elements, except for the layer elements of the present invention, are well known in the art and can be selected by the skilled person depending on the PV module desired.
The above-exemplified layer member may be a single layer member or a multilayer member other than the layer member of the present invention. Further, the other layer elements or portions of layers thereof may be produced in any order by extrusion (e.g., co-extrusion), by lamination, or by a combination of lamination or extrusion, as is known in the art, depending on the desired end application.
By "photovoltaic element" is meant that the element has photovoltaic activity. The photovoltaic element may be an element such as a photovoltaic cell, which has a well-known meaning in the art. Silicon-based materials (e.g., crystalline silicon) are non-limiting examples of materials for photovoltaic cells. As is well known to those skilled in the art, crystalline silicon materials can vary in crystallinity and crystal size. Alternatively, the photovoltaic element may be a substrate layer, on one of its surfaces applied other layers or deposits having photovoltaic activity, for example a glass layer, on one side of which an ink material having photovoltaic activity is printed; or depositing a material having photovoltaic activity on one side of the substrate layer. For example, in known thin-film solutions for photovoltaic elements, for example: the ink having photovoltaic activity is printed on one side of a substrate, which is typically a glass substrate.
The photovoltaic element is most preferably an element of a photovoltaic cell.
As mentioned above, "photovoltaic cell" refers herein to the aforementioned layer elements and connectors of the photovoltaic cell.
The detailed description given above for the layer element of the invention applies to the layer element present in the article, preferably a photovoltaic module.
In some embodiments of PV modules, there may also be adhesive layers between the different layer elements and/or between the layers of the multilayer element, as is known in the art. Such an adhesive layer has the function of improving the adhesion between two elements and is of well-known significance in the field of lamination. It will be apparent to those skilled in the art that the adhesive layer is different from other functional layer elements of the PV module (such as those specifically described above, below, or in the claims).
Preferably, there is no adhesive layer between the photovoltaic element and the front encapsulation layer element. Alternatively, preferably, there is no adhesive layer between the photovoltaic layer element and the layer element of the invention. More preferably, there is no adhesive layer between the photovoltaic element and the front encapsulation layer element and no adhesive layer between the photovoltaic layer element and the layer element of the invention.
The thicknesses of the above-described elements, as well as any other elements, of the inventive article (preferably a laminated photovoltaic module) can vary depending on the desired end-use application (e.g., desired photovoltaic module embodiment), as is well known in the PV art, and those skilled in the PV art can select these thicknesses accordingly.
By way of non-limiting example only, photovoltaic elements (e.g., elements of single crystal photovoltaic cells) typically have a thickness between 100 and 500 microns.
The thickness of layer a of the layer element of the Photovoltaic (PV) module of the invention, which preferably serves as a back encapsulant layer element, can naturally vary depending on the required PV module, as will be apparent to the skilled person. Typically, the thickness of layer a is as defined above. The back-encapsulation-layer-element may comprise, in addition to layer a, an additional layer X, when present, the back-encapsulation-layer-element may typically have a thickness of at most 2mm, preferably at most 1mm, typically 0.15 to 0.6mm. As mentioned above, naturally, the thickness depends on the desired end-use application and can be selected by the skilled person.
Similarly, the thickness of layer C of a layer element preferably used as protective back layer element (backsheet element) of the Photovoltaic (PV) module of the invention or as part of such protective back layer element is generally as defined together hereinabove. The protective back layer element may comprise an additional layer Y in addition to layer C, the thickness of which may naturally vary depending on the desired PV module application, as will be apparent to the skilled person. By way of example only, when layer Y is present, the protective backsheet element of a preferred PV module may typically have a thickness of at most 2mm, preferably at most 1mm, typically 0.15 to 0.6mm. Naturally, as mentioned above, the thickness depends on the desired end application and may be chosen by the skilled person.
The layer elements of the article, preferably of the photovoltaic module, can be produced as described above for the layer elements of the invention.
In addition to the layer elements of the invention, individual other elements of the PV module can be produced in a manner well known in the photovoltaic field or are commercially available.
Preparation method of photovoltaic module
The invention further provides a method for producing the assembly of the invention, wherein the method comprises the steps of:
-assembling the layer element of the invention and other layer elements into an assembly;
-laminating the components of the assembly at an elevated temperature to bond the components together; and
-recovering the obtained assembly.
The layer elements may be provided separately to the assembly step. Or, alternatively, a part of the layer element or a part of the layers of both layer elements may already be glued together, i.e. integrated, before being provided to the assembly step.
A preferred method for producing the assembly is a method of producing a Photovoltaic (PV) module by:
-assembling a photovoltaic element, a layer element of the invention and optionally further layer elements into a Photovoltaic (PV) module assembly;
-laminating the layer elements of the Photovoltaic (PV) module assembly at high temperature to bond the elements together; and
-recovering the Photovoltaic (PV) module obtained.
Conventional conditions and conventional equipment are well known and well described in the art of photovoltaic modules and can be selected by the skilled person.
As mentioned above, the partial layer elements may be in integrated form, i.e. more than two of said PV elements may be integrated together, for example by lamination, before the lamination process of the invention is carried out.
A preferred embodiment of a method of forming a preferred Photovoltaic (PV) module of the invention is a lamination method comprising:
-an assembly step of arranging the photovoltaic element and the layer element of the invention to form a multilayer assembly, wherein layer a of the layer element is arranged in contact with the photovoltaic element, preferably the assembly step arranges the front protective layer element, the front encapsulation layer element, the photovoltaic element and the layer element of the invention in the given order to form the multilayer assembly, wherein layer a of the layer element is arranged in contact with the photovoltaic element;
-a heating step of heating the formed PV module assembly, optionally and preferably in a chamber under evacuated conditions;
-a pressing step of building and maintaining pressure on the PV module assembly under heated conditions for assembly lamination; and
-a recycling step, cooling and removing the obtained PV module comprising the layer element.
The lamination process is carried out in a lamination apparatus, for example: any conventional laminator suitable for multilayer sheets to be laminated, such as laminators conventionally used in the production of photovoltaic modules. The selection of the laminator is within the skill of the technician. Typically, the laminator comprises chambers for heating, optional and preferred evacuation, pressing and recovery (including cooling) steps.
Use of
The use of a layer element according to the invention as defined above or below as an integrated backsheet element for a photovoltaic module, wherein the photovoltaic module comprises a photovoltaic element and said layer element, the photovoltaic element being in adhesive contact with layer a of the layer element.
The layer element and the photovoltaic module therefore preferably comprise the properties and definitions of the layer element and the photovoltaic module as described above or below.
Examples
Measurement method
Melt flow rate: the Melt Flow Rate (MFR) is determined according to ISO1133 in g/10min. MFR is an indication of the flowability and processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. MFR of Polypropylene 2 Measured at a temperature of 230 ℃ and a load of 2.16 kg. MFR of polyethylene 2 Measured at a temperature of 190 ℃ and under a load of 2.16 kg.
Density of: ISO 1183, measured on compression moulded plaques.
Comonomer content：
The content (wt% and mol%) of polar comonomer present in the ethylene copolymer (PE-a-B) and the content (wt% and mol%) of silane group-containing units present in the ethylene copolymer (PE-a), the ethylene copolymer (PE-a-B) and the ethylene copolymer (PE-B) were determined using the method in WO2018/141672 for the content (wt% and mol%) of polar comonomer present in the polymer (a) and the content (preferably comonomer) of silane group-containing units.
The content of alpha-olefin comonomer present in the ethylene copolymers (PE-B-a), ethylene copolymers (PE-B) and ethylene copolymers (PE-B-c) was determined using the method of WO 2019/134904 for the comonomer content of poly (ethylene-co-1-octene) copolymers.
Comonomer content present in the propylene polymer (PP-C-a) using the determination method of WO 2017/071847 for comonomer content.
Rheological properties:
dynamic shear stress determination (frequency sweep measurement)
Rheological PropertiesMeasured as described in WO 2018/141672.
m f Melting temperature (T) and Heat of fusion (H)Measured as described in WO 2018/141672.
Xylene Cold Soluble (XCS)Measured as described in WO 2018/141672.
Vicat softening temperatureMeasured according to ASTM D1525, method A (50 ℃/h, 10N).
Tensile modulus, tensile stress at yield and tensile strain at breakMeasured as described in WO 2018/141672.
Flexural modulusMeasured as described in WO 2017/071847.
Interlayer adhesion of coextruded films and laminates:
to test the adhesion of the coextruded films, a two-layer laminate was produced. The two coextruded films were laminated together with the sealant facing inward, with a teflon tape in the middle as the peel starting point. Vacuum lamination was carried out at 150 ℃ for a 5 minute evacuation time followed by 15 minutes pressurization with a chamber pressure of 800mbar.
Interlayer adhesion of coextruded/laminated sheets:
the adhesion of the coextruded/two-layer laminates was tested in a universal tester (Zwick Z010) according to the modified method of ISO 11339.
From each sample, 5 samples (length: about 200 mm/width: 25 mm) were prepared (cut) in the machine direction.
The teflon tape was removed, the separated layers were mounted between two pneumatic clamps, and the force required to pull and displace the layers was measured.
If peeling and yielding occur simultaneously, the elongated layers are slit to achieve pure peeling between the weakest interlayer.
The average peel force (in N) and the type of failure/point of failure were recorded.
In some cases, no peeling occurred, but the coextruded film only yielded.
The peeling results are classified into the following categories: "low" corresponds to an average peel force of <10N, "high" corresponds to a 30N result, and "very high" corresponds to a >60N result.
Testing parameters:
clamping distance: 10 mm
Preloading: 10N
Speed preloading: 50mm/min
Measuring the front and rear strokes: 20mm
Measuring stroke (including measuring forward and backward stroke): 100mm
Testing speed: 50mm/min
Power output measurement
The current-voltage (IV) characteristics of 1 cell module were obtained using a HALM cetisPV-Celltest3 flash tester. Prior to measurement, the system was calibrated using a reference cell with a known IV response. 1 cell of the battery module was flashed using a 30ms light pulse from a xenon gas source. All results of the IV measurements were automatically converted to Standard Test Conditions (STC) of 25 ℃ using PV Control software of HALM. Each sample set on both sides of the double-sided block was flashed 3 times and the average of these three individual measurements was calculated from the given IV parameters. When flashing from the front, all modules were flash tested using a mask. No mask is used for the flash from the back. The black mask was made of standard black colored paper with 160 x 160mm square openings. During the flash test, the black mask was positioned such that the solar cells in the solar module were fully exposed to the flash pulse with a 2mm gap between the edge of the solar cell and the black mask. The black mask was fixed on the module using tape. All IV characterizations were performed according to the IEC 60904 series.
The reserved Pmax is determined according to IEC 60904. Pmax is the photovoltaic module from 1000W/m under Standard Test Conditions (STC) 2 The power generated by the flash pulse. From the IV curve generated by the flash test, pmax can be obtained by the following equation, where Isc is the short circuit current, voc is the open circuit voltage, and FF is the fill factor.
P max ＝V oc *I sc *FF
EL imaging
The solar micromodules placed in the dark room were supplied with current and the emitted light was detected using a NIKON D5200 camera, which selected f-number f/5, exposure time 20 seconds and ISO 3200 sensitivity.
Damp-heat test (DH)
The PV micromodules of the invention were subjected to a moist heat (DH) test. The DH test was carried out according to IEC 61215 in a climatic chamber at a temperature of 85 ℃ and a relative humidity of 85% for 2000 hours. Optical inspection, EL imaging and power output testing were then performed to evaluate the PV micromodules.
Thermal Cycling Test (TCT) for photovoltaic micromodules
And carrying out thermal cycle test on the photovoltaic micro-module. According to IEC 61215, the samples were placed in a climatic chamber at a temperature between-40 ℃ and 85 ℃.50 cycles per week according to the guidelines given in the standards. The micromodules were subjected to a total of 250 cycles in the climatic chamber. Optical inspection, EL imaging and power output testing were then performed to evaluate the PV micromodules.
Thermal Cycle Test (TCT)
An additional test run was performed on the backsheet layer alone to evaluate the durability of the composition. A250 μm single film was produced. Small holes were pressed in MD, TD and 45 ° directions with a cutting tool to provide starting points for crack propagation. Laminates with glass, EVA sealant and a single layer backsheet film of the composition of the invention were then produced to evaluate performance. According to IEC 61215, the samples were placed in a climatic chamber at a temperature between-40 ℃ and 85 ℃. The cycles were performed 50 times per week according to the guidelines given in the standards. The laminate was subjected to a total of 250 cycles in a climate chamber. A visual inspection was then performed to assess possible crack propagation.
Experimental part
Preparation of the polyethylene composition for layer A (PE-A)
Ethylene copolymers (PE-A-b) were produced in commercial high pressure tubular reactors using conventional peroxide initiators at pressures of 2500-3000bar with maximum temperatures of 250-300 ℃. Ethylene monomer, methyl Acrylate (MA) polar comonomer and Vinyltrimethoxysilane (VTMS) comonomer (silane group containing comonomer) are added to the reactor system in a conventional manner. As is well known to the skilled person, the MFR is adjusted using CTA. After having obtained the information of the property balance required for the final polymer (a) of the invention, the skilled person can control the process for obtaining the ethylene copolymer (PE-a-b).
Amount of vinyltrimethoxysilane units VTMS (= silane group-containing units), amount of MA and MFR 2 Given in table 1.
The properties in the table below were measured on the basis of the polymer (a) obtained from the reactor or on the basis of the layer samples obtained as shown below.
Table 1: properties of the ethylene copolymer (PE-A-b) obtained from the reactor
| Testing polymers | Ethylene copolymer (PE-A-b) |
| MFR 2,16 ,g/10min | 3.5 |
| Content of Methyl Acrylate (MA), mol% (% by weight) | 8.8(22.5) |
| Melting temperature of | 91 |
| VTMS content, mol% (% by weight) | 0.3(1.4) |
| Density, kg/m 3 | 948 |
| SHI(0.05/300)，150℃ | 70 |
In table 1 above, MA represents the amount of methyl acrylate comonomer units present in the polymer and VTMS represents the amount of vinyltrimethoxysilane comonomer units present in the polymer.
The ethylene copolymer (PE-a-b) is compounded to produce the polyethylene composition for layer a (PE-a).
Polyethylene composition 1 (PE-A-1)Consisting of the above polyethylene composition (PE-A-b).
Polyethylene composition 1 (PE-A-2)Consisting of 90% by weight of the above polyethylene composition (PE-A-b) and 10% by weight of TiO 2 A masterbatch composition ofThe masterbatch comprises 65% by weight of TiO 2 。
Preparation of polyethylene composition for layer B (PE-B)
Polyethylene composition 1 (PE-B-1)Consisting of Queo7007LA, a vinyl plastomer with 1-octene comonomer units, melt flow rate MFR 2 (190 ℃,2.16 kg) is 6.5g/10min, and the density is 870kg/m 3 (including stabilizers) commercially available from northern Europe chemical company.
Polyethylene composition 2 (PE-B-2)Consisting of Queo7007LA, which is grafted with 1% by weight of vinyltrimethoxysilane units (VTMS). Grafting was carried out as described in the example section of WO 2019/201934.
Polyethylene composition 3 (PE-B-3)Consisting of Queo7001LA which is an ethylene based plastomer having 1-octene comonomer units, melt flow rate MFR 2 (190 ℃,2.16 kg) is 1.0g/10min, and the density is 870kg/m 3 (including stabilizers) commercially available from northern Europe chemical company.
Preparation of the Polypropylene composition for layer C (PE-C)
ForPolypropylene composition (PP-C-1)The composition described in example IE6 according to WO 2017/071847 was used.
The polypropylene composition thus comprises:
40.7% by weight of a heterophasic propylene copolymer B,
27.2% by weight of a heterophasic propylene copolymer A,
(both prepared as described in the example section of WO 2017/071847)
23% by weight of talc, the talc being,
8 wt% Queo 8230, a commercial Nordic chemical company, an ethylene based octene plastomer produced in a solution polymerization process using a metallocene catalyst, MFR 2 (190 ℃) 30g/10min, and the density 882kg/m 3 And are and
1.1% by weight of additive, as described in the example section of WO 2017/071847.
For thePolypropylene composition (PP-C-2)Except for the polypropylene composition (In addition to the additives added in PP-C-1), the following pigments were also added in the melt homogenization step:
7% by weight of TiO 2 Masterbatch comprising 70 wt% TiO 2 。
The polypropylene composition (PP-C-1) had the properties as listed in Table 3 below. Tensile properties such as tensile modulus, tensile strength and tensile strain at break were measured in the MD direction using a 200 μm monolayer cast film.
Table 3: properties of the Polypropylene composition (PP-C-1)
Since the polypropylene composition (PP-C-2) differs from the polypropylene composition (PP-C-1) only in the presence of TiO 2 Masterbatch, it is therefore possible to expect the same properties as the polypropylene composition (PP-C-1).
Preparation of layer elements
Layer A is made of a polyethylene composition (PE-A-1) and a polyethylene composition (PE-A-2). Layer B is made of a polyethylene composition (PE-B-1), a polyethylene composition (PE-B-2) and a polyethylene composition (PE-B-3). Layer C is made of a polypropylene composition (PP-C-1) and a polypropylene composition (PP-C-2).
A 3-layer calendered film for the inventive layer elements of examples IE1 to IE5 and a 2-layer cast film for the comparative layer element of comparative example CE1 were prepared using a dr.
The individual layers were extruded with separate extruders: the two outer layers (layer A and layer C) were extruded with an extruder equipped with a 25mm screw and an LD of 30. The core layer (layer B) was extruded with an extruder equipped with a 30mm screw and an LD of 30. The thickness of each of the layers A and B was 225 μm, and the thickness of each of the layers C was 250 μm, so that the film thicknesses of the inventive examples IE1 to IE5 were 700 μm, and the film thickness of the comparative example CE1 was 475 μm.
Layer a is extruded onto the embossed side of the calendering unit and layer C is extruded onto the smooth side of the calendering unit, sandwiching layer B between layer a and layer C if present. The die extruder was fixed at a 90 ° angle and extruded onto a chill roll. The melt will be extruded between the nip of two steel rolls, which are pre-adjusted to a gap of about 600 microns by a feeler gauge before starting the line. One roller used the pyramidal embossing structure (layer a side) and the other roller was a polished standard chill roller (layer C side). The rolls were pressed against each other with a hydraulic pressure of 75bar to transfer the structure to the membrane. The chill roll was cooled to 25 ℃. The polyethylene compositions (PE-A) and (PE-B) have a melting temperature of 140 to 190 ℃ and the polypropylene compositions PP-C have a melting temperature of 210 to 215 ℃. Each extruder was operated at a throughput of 5 to 20 kg/h. The width of the die was 300 mm.
Table 4 shows the following coextruded layer elements:
table 4: co-extruded layer element
Preparation of the laminate
Production of a two-layer laminate of each example layer element LE: LE/LE, layers a opposite each other and with a teflon tape at one end of the laminate to provide the starting point for the following peel test. T-peel testing was performed on 25mm wide strips with a preload of 10N and a test speed of 50mm/min. The results are reported in table 5 below. Average peel force F AVG Recording is performed in the following manner: compared with peeling (weak) by hand<10N is a "low" value, a "high" corresponds to a value of>30N, "very high" corresponds to a value of>60N, which is considered to be a strong adhesive force. If no results are given, no peeling is observed.
Table 5: t-peel test results for IBS bilaminates before and after 1000 hours DH.
Preparation of photovoltaic micromodules
For PV modules comprising the above layer elements as integrated backsheet elements, a 300mm x 200mm laminate consisting of glass/sealant/cells with connectors/layer elements as described above was prepared using a PEnergy L036LAB vacuum laminator.
Glass layer, structured solar glass, low-iron glass, provided by interboat, length: 300mm, width: 200mm and the total thickness is 3.2mm.
Before placing the first encapsulant element film on the solar glass, the front protective glass element was cleaned with isopropyl alcohol. The front encapsulant layer elements are cut to the same size as the solar glass elements. After the front encapsulant element is placed on the front protective glass element, the soldered solar cells are then placed on the front encapsulant element. Further, the layer element of the invention is placed on the obtained PV cell element. The resulting PV module assembly is then subjected to a lamination process as described below.
Table 6: lamination arrangement for photovoltaic modules
The following composition was used as the front sealant:
EVA: (Hangzhou EVA F406P): vinyl acetate, 28% vinyl acetate, MFR 2 = about 35g/10minPE-a-b: (thickness 0.45 mm): ethylene terpolymer having methyl acrylate comonomer units and vinyltrimethoxysilane comonomer units, i.e. 22.5 wt% MA, 1.4% VTMS, MFR 2 =2.5 to 3.5g/10min, including UV stable hindered amine compounds (CAS number: 65447-77-0).
All cells used the same type of structured solar glass with a thickness of 3.2mm (Ducat).
The cell used was a P-type single crystal silicon cell with three bus bars, dimensions 156x156x0.2 mm, and a cell efficiency of 17.80%. The battery is supplied by the ITS, part number ITS2-02-60MS3B200C-1780B. The solder wire comprises Sn, pb, ag (62.
Vacuum lamination was carried out at 150 ℃ using the following lamination procedure: evacuation time of 5 minutes followed by 15 minutes pressurization was carried out, the upper chamber pressure being 800mbar.
The power output (forward flash only) of the produced photovoltaic modules was tested before and after the aging test (2000 h DH and 2000h DH +250 cycles TCT) and reported in table 6. The associated power loss after each burn-in test is reported in brackets next to the power output. Table 7 reports the visual inspection and EL imaging results after these micromodules were aged.
Table 7: power output and power loss of the modules before and after DH and TCT burn-in tests.
* Power loss in% compared to the initial value.
Table 8: visual (and EL image) inspection of aged modules
Backboard durability test flow
An additional test run was performed on the backsheet layer alone to evaluate the durability of the composition in the critical TCT test. Comparing the different compounds with PP-C-1, PP-C-1 has been evaluated as excellent in the TCT test. A 250 μm monolayer backsheet film of each composition was produced on a Dr Collin line similar to that described above, using only one extruder and without surface indentation (melt temperature 210 to 215 ℃, chill roll temperature 25 ℃). Small holes were pressed in MD, TD and 45 ° directions with a cutting tool to provide starting points for crack propagation. A laminate of a single layer backsheet film with glass, EVA encapsulant (same as above) and the following inventive composition was then prepared to evaluate performance in the TCT test. The same lamination conditions as described above were used. Visual inspection was performed after 200 cycles of TCT testing. The reference PP-C-1 sample showing cracks at the most severe corners but crack propagation less than 2mm long was rated as good (++), the sample with fewer cracks was rated as very good (++), and the sample with a little more cracks was rated as good (+)
In table 9 below, the evaluation of the results of the different test compositions (in weight%) and the 200-cycle thermal cycle test are shown.
Table 9: PP-C layer composition (wt%) and TCT test performance.
| PP-C-1 | PP-C-3 | PP-C-4 | PP-C-5 | |
| Heterophasic copolymer A | 27.2 | 28.5 | 63.6 | 32.5 |
| Heterophasic copolymer B | 40.7 | 42 | - | 45 |
| Talc | 23 | 10 | 10 | 10 |
| Queo 8230 | 8 | 9 | - | 7 |
| Queo 6800 | - | - | 16 | - |
| Additive agent | 1.1 | 1.1 | 1.1 | 1.1 |
| TiO 2 Master batch | 10 | 10 | 7 | |
| TCT test Performance (200 cycles) | ++ | + | +++ | +++ |
Heterophasic copolymer AAs described above on page 52
Heterophasic copolymer BAs described above on page 52
Both prepared as described in the example section of WO 2017/071847
Queo 8230Is a copolymer of ethylene and 1-octene (MFR determined according to ISO 1133) 2 190 ℃ =30.0g/10min, density =883kg/m determined according to ISO 1183-1/A 3 ) Commercially available from northern Europe chemical company (AT).
Queo 6800LAIs a copolymer of ethylene and 1-octene (MFR determined according to ISO 1133) 2 190 ℃ =0.5g/10min, density =868kg/m determined according to ISO 1183-1/A 3 ) Commercially available from northern Europe chemical company (AT).
Claims (15)
1. A layer element comprising at least three layers A, B and C constructed in A-B-C, wherein,
-layer a comprises a polyethylene composition (PE-a) comprising an ethylene copolymer selected from the group consisting of:
-an ethylene copolymer having silane group-containing units (PE-a); or
-copolymers of ethylene with polar comonomer units (PE-A-b), said polar comonomer units being selected from (C) 1 -C 6 ) Alkyl acrylates or (C) 1 -C 6 ) Alkyl (C) 1 -C 6 ) -one or more alkyl acrylate comonomer units, said copolymer (PE-A-b) additionally having silane group(s) containing units,
thus, the ethylene copolymer (PE-A-a) is different from the ethylene copolymer (PE-A-b);
-layer B comprises a polyethylene composition (PE-B) comprising an ethylene copolymer selected from the group consisting of:
a density of 850kg/m 3 To 905kg/m 3 A comonomer unit selected from one or more alpha-olefins having from 3 to 12 carbon atoms (PE-B-a); or
A density of 850kg/m 3 To 905kg/m 3 A copolymer of ethylene and comonomer units selected from one or more alpha-olefins having 3 to 12 carbon atoms (PE-B) additionally having silane group(s) containing units; or alternatively
-density of 850kg/m 3 To 905kg/m 3 A copolymer of ethylene and comonomer units selected from one or more alpha-olefins having from 3 to 12 carbon atoms (PE-B-c), said copolymer (PE-B-c) additionally having functional group containing units derived from at least one unsaturated carboxylic acid and/or anhydride, metal salt, ester, amide or imide thereof and mixtures thereof; and
-layer C comprises a polypropylene composition (PP-C) comprising a propylene polymer (PP-C-a), wherein layer a and layer B, and layer B and layer C are in adhesive contact with each other.
2. The layer element according to claim 1, wherein the polar comonomer units in the ethylene copolymer (PE-a-b) are selected from (C) 1 -C 6 ) -alkyl acrylate comonomer units.
3. The layer element according to claim 1 or 2, wherein the silane group containing units of the ethylene copolymer (PE-a) or the ethylene copolymer (PE-a-b) are hydrolysable unsaturated silane compounds represented by the following formula (I):
R 1 SiR 2 q Y 3-q (I)
in the formula (I), the compound is shown in the specification,
R 1 is an ethylenically unsaturated hydrocarbon group, a hydrocarbyloxy group or a (meth) acryloyloxyalkyl group,
each R 2 Independently an aliphatic saturated hydrocarbon group,
y, which may be identical or different, is a hydrolyzable organic radical, and
q is 0, 1 or 2.
4. The layer element according to any one of claims 1 to 3, wherein the ethylene copolymer (PE-A-a) and the ethylene copolymer (PE-A-b) have one or more of the following properties:
a density of 920 to 960kg/m 3 ；
Melt flow Rate MFR 2 Less than 20g/10min;
-a melting temperature Tm of 70 to 120 ℃; and/or the presence of a gas in the gas,
shear thinning index SHI 0.05/300 Is 30.0 to 100.0.
5. The layer element according to any one of claims 1 to 4, wherein the ethylene copolymer (PE-B-a) is a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene;
the ethylene copolymer (PE-B-B) is a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene, to which silane group-containing units are grafted; and
the ethylene copolymer (PE-B-c) is a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene onto which functional group-containing units derived from maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, fumaric anhydride, maleic acid, citraconic acid and mixtures thereof are grafted.
6. The layer element according to any one of claims 1 to 5, wherein the silane group containing units of the ethylene copolymer (PE-A-b) are hydrolysable unsaturated silane compounds represented by the following formula (I):
R 1 SiR 2 q Y 3-q (I)
in the formula (I), the compound is shown in the specification,
R 1 is an ethylenically unsaturated hydrocarbon group, a hydrocarbyloxy group or a (meth) acryloyloxyalkyl group,
each R 2 Independently an aliphatic saturated hydrocarbon group,
y, which may be identical or different, is a hydrolyzable organic group, and
q is 0, 1 or 2.
7. The layer element of any of claims 1 to 6, wherein the melt flow rate MFR of the ethylene copolymer (PE-B-a), the ethylene copolymer (PE-B-B) or the ethylene copolymer (PE-B-c) 2 Less than 20g/10min.
8. The layer element according to any one of claims 1 to 7, wherein the polypropylene composition (PP-C) comprises a heterophasic propylene copolymer comprising:
a polypropylene matrix component, and
-an elastomeric propylene copolymer component dispersed in the polypropylene matrix.
9. The layer element according to claim 8, wherein the heterophasic propylene copolymer has one or more of the following properties:
-a melting temperature Tm of at least 145 ℃;
-a Vicat softening temperature Vicat a of at least 90 ℃;
melt flow Rate MFR 2 1.0 to 20.0g/10min;
-the amount of Xylene Cold Soluble (XCS) fraction is from 5 to 40 wt%;
-comonomer content from 2.0 to 20.0 wt.%;
-a flexural modulus of at least 600MPa; and/or
A density of 900 to 910kg/m 3 。
10. The layer element as claimed in any one of claims 1 to 9, wherein the layer a: layer B: layer C has a thickness ratio of 45: layer A: layer B: layer C: the thickness ratio of layer Y is 20.
11. The layer element as claimed in one of claims 1 to 10, wherein the overall thickness of the layer element is 325 μ ι η to 2000 μ ι η.
12. An article comprising the layer element of any one of claims 1 to 11, preferably a photovoltaic module comprising a photovoltaic element and the layer element, wherein the photovoltaic element is in adhesive contact with layer a of the layer element; more preferably the photovoltaic module comprises, in the given order, a protective front layer element, a front encapsulation layer element, a photovoltaic element and an integrated backsheet element comprising, preferably consisting of, said Layer Element (LE).
13. Method for producing a layer element according to any one of claims 1 to 11, comprising the steps of:
-bonding the layers a, B and C of the layer element in a configuration a-B-C by extrusion or lamination; and
-recovering the formed layer element.
14. A method of producing an article that is the Photovoltaic (PV) module of claim 12, the method comprising the steps of:
-assembling the photovoltaic element, the layer element and optionally further layer elements into a Photovoltaic (PV) module assembly;
-laminating the layer elements of the Photovoltaic (PV) module assembly at high temperature to bond the elements together; and
-recovering the Photovoltaic (PV) module obtained.
15. Use of the layer element of any one of claims 1 to 11 as an integrated backsheet element of a photovoltaic module comprising a photovoltaic element and the layer element, the photovoltaic element being in adhesive contact with layer a of the layer element.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20176219.2A EP3915782A1 (en) | 2020-05-25 | 2020-05-25 | Layer element suitable as integrated backsheet element of a photovoltaic module |
| EP20176219.2 | 2020-05-25 | ||
| PCT/EP2021/062245 WO2021239445A1 (en) | 2020-05-25 | 2021-05-10 | Layer element suitable as integrated backsheet element of a photovoltaic module |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115666938A true CN115666938A (en) | 2023-01-31 |
Family
ID=70847242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180037440.2A Pending CN115666938A (en) | 2020-05-25 | 2021-05-10 | Layer element suitable as an integrated back sheet element of a photovoltaic module |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20230212379A1 (en) |
| EP (1) | EP3915782A1 (en) |
| CN (1) | CN115666938A (en) |
| WO (1) | WO2021239445A1 (en) |
Family Cites Families (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107414A (en) | 1971-06-25 | 1978-08-15 | Montecatini Edison S.P.A. | Process for the stereoregular polymerization of alpha olefins |
| US4226963A (en) | 1971-06-25 | 1980-10-07 | Montedison S.P.A. | Process for the stereoregular polymerization of alpha-olephins |
| US4186107A (en) | 1978-04-14 | 1980-01-29 | Hercules Incorporated | Solid catalyst component for olefin polymerization |
| US4347160A (en) | 1980-06-27 | 1982-08-31 | Stauffer Chemical Company | Titanium halide catalyst system |
| IT1209255B (en) | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| JPS57153005A (en) | 1981-03-19 | 1982-09-21 | Ube Ind Ltd | Polymerization of alpha-olefin |
| US4530912A (en) | 1981-06-04 | 1985-07-23 | Chemplex Company | Polymerization catalyst and method |
| EP0072129B2 (en) | 1981-08-07 | 1990-02-28 | Imperial Chemical Industries Plc | Supported transition metal composition |
| US4382019A (en) | 1981-09-10 | 1983-05-03 | Stauffer Chemical Company | Purified catalyst support |
| IT1190682B (en) | 1982-02-12 | 1988-02-24 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1190681B (en) | 1982-02-12 | 1988-02-24 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1190683B (en) | 1982-02-12 | 1988-02-24 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| US4532313A (en) | 1982-10-13 | 1985-07-30 | Himont Incorporated | Method for preparing an improved catalyst support, Ziegler-Natta catalyst utilizing said support and polymerization of 1-olefins utilizing said catalyst |
| US4560671A (en) | 1983-07-01 | 1985-12-24 | Union Carbide Corporation | Olefin polymerization catalysts adapted for gas phase processes |
| US4581342A (en) | 1984-11-26 | 1986-04-08 | Standard Oil Company (Indiana) | Supported olefin polymerization catalyst |
| US4657882A (en) | 1984-11-26 | 1987-04-14 | Amoco Corporation | Supported olefin polymerization catalyst produced from a magnesium alkyl/organophosphoryl complex |
| FI80055C (en) | 1986-06-09 | 1990-04-10 | Neste Oy | Process for preparing catalytic components for polymerization of olefins |
| FI86867C (en) | 1990-12-28 | 1992-10-26 | Neste Oy | FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN |
| FI88049C (en) | 1991-05-09 | 1993-03-25 | Neste Oy | Large pore polyolefin, process for its preparation and a catalyst used in the process |
| FI88047C (en) | 1991-05-09 | 1993-03-25 | Neste Oy | Catalyst-based catalyst for polymerization of olivines |
| FI88048C (en) | 1991-05-09 | 1993-03-25 | Neste Oy | Coarse-grained polyolefin, its method of preparation and a catalyst used in the method |
| FI90247C (en) | 1991-05-31 | 1994-01-10 | Borealis As | Process for the preparation of active and uniform carrier particles for polymerization catalysts |
| FI91967C (en) | 1991-11-29 | 1994-09-12 | Borealis Polymers Oy | Process for the preparation of olefin polymerization catalysts |
| FI90248C (en) | 1991-11-29 | 1994-01-10 | Borealis As | A process for preparing a particulate support for an olefin polymerization catalyst |
| FI95715C (en) | 1992-03-24 | 1996-03-11 | Neste Oy | Preparation of polymerization catalyst support prepared by spray crystallization |
| FI96214C (en) | 1994-05-31 | 1996-05-27 | Borealis As | Stereospecific catalyst system for the polymerization of olefins |
| FI102070B (en) | 1996-03-29 | 1998-10-15 | Borealis As | A new complex compound, its preparation and use |
| FI963707A0 (en) | 1996-09-19 | 1996-09-19 | Borealis Polymers Oy | Free polymerization of an alpha-olefin, by polymerization with an optional catalyst and further preparation of a polymer |
| FI111848B (en) | 1997-06-24 | 2003-09-30 | Borealis Tech Oy | Process and equipment for the preparation of homopolymers and copolymers of propylene |
| FI974175A (en) | 1997-11-07 | 1999-05-08 | Borealis As | Process for producing polypropylene |
| FI980342A0 (en) | 1997-11-07 | 1998-02-13 | Borealis As | Polymerroer och -roerkopplingar |
| WO1999033842A1 (en) | 1997-12-23 | 1999-07-08 | Borealis Technology Oy | Product containing magnesium, halogen and alkoxy |
| FI991057A0 (en) | 1999-05-07 | 1999-05-07 | Borealis As | High stiffness propylene polymers and process for their preparation |
| ES2266053T3 (en) | 2001-06-20 | 2007-03-01 | Borealis Technology Oy | PREPARATION OF A CATALYST COMPONENT FOR OLEFINE POLYMERIZATION. |
| EP1270610B8 (en) | 2001-06-20 | 2006-09-27 | Borealis Technology Oy | Preparation of olefin polymerisation catalyst component |
| US20060052541A1 (en) | 2002-06-25 | 2006-03-09 | Erling Hagen | Polyolefin with improved scratch resistance and process for producing the same |
| EP1403292B1 (en) | 2002-09-30 | 2016-04-13 | Borealis Polymers Oy | Process for preparing an olefin polymerisation catalyst component with improved high temperature activity |
| EP1484343A1 (en) | 2003-06-06 | 2004-12-08 | Universiteit Twente | Process for the catalytic polymerization of olefins, a reactor system and its use in the same process |
| ES2525554T3 (en) | 2010-07-13 | 2014-12-26 | Borealis Ag | Catalyst component |
| EP2726283B1 (en) * | 2011-06-30 | 2015-08-19 | Dow Global Technologies LLC | Multilayered polyolefin-based films having a layer comprising a crystalline block copolymer composite or a block copolymer composite resin |
| EP2610271B1 (en) | 2011-12-30 | 2019-03-20 | Borealis AG | Preparation of phthalate free ZN PP catalysts |
| WO2015199925A1 (en) * | 2014-06-24 | 2015-12-30 | Dow Global Technologies Llc | Polyolefin photovoltaic backsheet comprising a stabilized polypropylene layer |
| TWI609908B (en) * | 2014-09-18 | 2018-01-01 | 柏列利斯股份公司 | Polymer composition for a layer of a layer element |
| WO2017071847A1 (en) | 2015-10-28 | 2017-05-04 | Borealis Ag | Polypropylene composition for a layer element |
| AU2018216859B2 (en) | 2017-02-01 | 2020-07-23 | Borealis Ag | Article comprising a layer element |
| KR20200083636A (en) | 2018-01-05 | 2020-07-08 | 보레알리스 아게 | Polypropylene composition with improved sealing behavior |
| WO2019201934A1 (en) | 2018-04-16 | 2019-10-24 | Borealis Ag | A multilayer element |
-
2020
- 2020-05-25 EP EP20176219.2A patent/EP3915782A1/en active Pending
-
2021
- 2021-05-10 CN CN202180037440.2A patent/CN115666938A/en active Pending
- 2021-05-10 WO PCT/EP2021/062245 patent/WO2021239445A1/en active Application Filing
- 2021-05-10 US US17/926,666 patent/US20230212379A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US20230212379A1 (en) | 2023-07-06 |
| WO2021239445A1 (en) | 2021-12-02 |
| EP3915782A1 (en) | 2021-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8431235B2 (en) | Co-extruded, multilayered polyolefin-based backsheet for electronic device modules | |
| CN110713803B (en) | Thermoplastic photovoltaic module packaging adhesive film and preparation method thereof | |
| KR102027990B1 (en) | Multilayered polyolefin-based films having a layer comprising a crystalline block copolymer composite or a block copolymer composite resin | |
| KR101617898B1 (en) | Binder based on carboxylic acid vinyl ethylene ester copolymer and polyolefin containing a functional monomer | |
| EP3143645B1 (en) | Polypropylene composition for producing a layer of a photovoltaic module | |
| WO2018033006A1 (en) | Extruded solar power back panel and manufacturing method thereof | |
| AU2018216859B2 (en) | Article comprising a layer element | |
| JP2014506938A (en) | Silane-containing thermoplastic polyolefin copolymer resin, film, method for producing the same, and photovoltaic module laminate structure including the resin and film | |
| KR20130093611A (en) | Multilayer structures containing a fluorinated copolymer resin layer and an ethylene terpolymer layer | |
| EP3212700B1 (en) | Pv module with film layer comprising micronized silica gel | |
| KR20160002793A (en) | Electronic devices comprising two encapsulant films | |
| US20230197871A1 (en) | Layer element suitable as integrated backsheet for a bifacial photovoltaic module | |
| CN115666938A (en) | Layer element suitable as an integrated back sheet element of a photovoltaic module | |
| CN115720550A (en) | Polymer compositions with improved storage stability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |